CN105504157B - Low-tension hydroxyl oximido emulsion flooding polymers and preparation method thereof - Google Patents
Low-tension hydroxyl oximido emulsion flooding polymers and preparation method thereof Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 63
- 239000000839 emulsion Substances 0.000 title claims abstract description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 241000195493 Cryptophyta Species 0.000 claims abstract description 13
- 150000001408 amides Chemical class 0.000 claims abstract description 13
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 13
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims abstract description 12
- XWNSFEAWWGGSKJ-UHFFFAOYSA-N 4-acetyl-4-methylheptanedinitrile Chemical compound N#CCCC(C)(C(=O)C)CCC#N XWNSFEAWWGGSKJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 10
- 239000004153 Potassium bromate Substances 0.000 claims abstract description 10
- 239000004280 Sodium formate Substances 0.000 claims abstract description 10
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims abstract description 10
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims abstract description 10
- 229940094037 potassium bromate Drugs 0.000 claims abstract description 10
- 235000019396 potassium bromate Nutrition 0.000 claims abstract description 10
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 10
- 239000011734 sodium Substances 0.000 claims abstract description 10
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims abstract description 10
- 235000019254 sodium formate Nutrition 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims description 11
- 150000007513 acids Chemical class 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 7
- NLMKTBGFQGKQEV-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-hexadecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO NLMKTBGFQGKQEV-UHFFFAOYSA-N 0.000 claims description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- WTBIAPVQQBCLFP-UHFFFAOYSA-N N.N.N.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O Chemical compound N.N.N.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O WTBIAPVQQBCLFP-UHFFFAOYSA-N 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims 1
- -1 acrylamido Chemical group 0.000 abstract description 3
- 239000004530 micro-emulsion Substances 0.000 abstract description 3
- 239000012263 liquid product Substances 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- FFSJITPWJCNADF-UHFFFAOYSA-N CCCCCCCCCCCCCCCC[O] Chemical compound CCCCCCCCCCCCCCCC[O] FFSJITPWJCNADF-UHFFFAOYSA-N 0.000 abstract 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 abstract 1
- BRXCDHOLJPJLLT-UHFFFAOYSA-N butane-2-sulfonic acid Chemical compound CCC(C)S(O)(=O)=O BRXCDHOLJPJLLT-UHFFFAOYSA-N 0.000 abstract 1
- 229920000136 polysorbate Polymers 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 71
- 239000000243 solution Substances 0.000 description 30
- 239000004908 Emulsion polymer Substances 0.000 description 27
- 238000006073 displacement reaction Methods 0.000 description 24
- 238000011084 recovery Methods 0.000 description 19
- 238000000034 method Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000010008 shearing Methods 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011435 rock Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010729 system oil Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 150000003626 triacylglycerols Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical group C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 description 1
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 238000010793 Steam injection (oil industry) Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/32—Polymerisation in water-in-oil emulsions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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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
- C09K8/584—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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Polymers & Plastics (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of low-tension hydroxyl oximido emulsion flooding polymers and preparation method thereof, wherein, the low-tension hydroxyl oximido emulsion flooding polymers are composed of the following components：Acrylamide, acrylic acid, water, liquid caustic soda, the methyl propane sulfonic acid of 2 acrylamido 2, methylene bisacrylamide amine, potassium bromate, sodium formate, the sodium of diethylene triamine pentacetic acid (DTPA) five, cupric sulfate pentahydrate, HAS, white oil D110, algae oil acid amides, Span 80, Tween 81, emulsifying dispersant OA90, azo, isomery cetyl oxygen vinethene.Low-tension hydroxyl oximido emulsion flooding polymers of the present invention have HMW, high solids content, assign the good multi-functional stability of high polymer main chain, low-tension, the reverse microemulsion liquid product of instant capacity.
Description
Technical field
The present invention relates to organic polymer new chemical materialses technical field, more particularly to a kind of low-tension hydroxyl oximido emulsion flooding
Oil polymer and preparation method thereof.
Background technology
Oil is a kind of non-renewable fossil energy, and its recovery ratio is petroleum industrial circle, or even whole industrial quarters is closed the most
The problem of heart.In oil exploitation, it is called primary oil recovery with oil reservoir natural energy exploitation oil, recovery ratio is general in this case
It can only achieve 15% or so.Later stage uses the mode such as water filling or non-mixed phase gas injection, can improve formation pressure and the original of displacement oil reservoir
Oil, this method are called secondary oil recovery.Secondary oil recovery can reach 30%-40% recovery ratio, even as high as 80% at present.But with
The continuous injection of dampening, when the moisture content in oil field brings up to more than 90%, it is uneconomic to continue water filling.
Most of oil field in China, such as Daqing oil field, has undergone the exploitation in more than 50 years, has arrived late high water content period,
Comprehensive water cut is recovered the oil close to 93%, equivalent to involving swab in oil prospecting, water in water, how produced remaining residual more under these conditions
Oil, it is one of most concerned problem of current industrial quarters.
By injecting chemical substance or microorganism, so as to change the oil property of oil reservoir and improve formation pressure, driven
Oil, this is referred to as tertiary oil recovery, or intensified oil reduction（Enhanced Oil Recovery, abbreviation EOR）.The reinforcing of main flow is adopted at present
Oily method includes heat extraction by steam injection, carbon dioxide mixed phase drives, hydrocarbon mixed phase drives, polymer flooding.In China, first-elected reinforcing is adopted
Oil tech is polymer flooding, and China works out ternary composite driving and foam composite flooding in succession, so as to improve oil recovery.
But these polyacrylamide polymers displacement of reservoir oil products used at present, it is slow, solution homogeneous to there is dissolution velocity
Property and the problems such as poor fluidity, Efficient Adhesive Promotion be poor, oil displacement efficiency difference, therefore it is eager need to research and develop high viscosity, low-tension,
New high-efficiency emulsion polymer displacement of reservoir oil product, passes through the Unique physical design being copolymerized containing poly modified functional group and emulsion polymerization side
Formula, in emulsion polymerization process introduce with emulsification function, phase stabilization function, containing surface reactive material polymerization member, crosslinking member,
Salt resistance member, to realize that the quick dissolving of emulsion flooding oil product, thickening are anti-shearing, effectively reduce emulsion polymer displacement of reservoir oil product system
Interfacial tension, improve the mobility and washing oil ability of solution, improve oil recovery rate.
The content of the invention
In view of this, the present invention provides a kind of low-tension hydroxyl oximido emulsion flooding polymers and preparation method thereof, using elder generation
The hydroxyl oximate water solubility multi-component copolymer reverse microemulsion liquid preparing process entered, and introduce a variety of functional groups such as on high polymer main chain
Amide groups, hydroxyl and hydroxamic group etc., while be implanted into algae oil acid amides overlength carbochain surfactant, then with methylene bisacrylamide acyl
Amine crosslinker, salt resistance monomer 2- acrylamide-2-methylpro panesulfonic acids（AMPS）Copolymerization, so as to prepare a kind of HMW,
High solids content, the good multi-functional stability of high polymer main chain, low-tension, the reverse microemulsion liquid product of instant capacity are assigned, effectively
Ground overcomes or avoids shortcoming present in above-mentioned prior art or deficiency.
The present invention is solved the above problems by following technological means：
Low-tension hydroxyl oximido emulsion flooding polymers, it is composed of the following components：Acrylamide, acrylic acid, water, liquid caustic soda, 2-
Acrylamide-2-methylpro panesulfonic acid, methylene-bisacrylamide, potassium bromate, sodium formate, the sodium of diethylene triamine pentacetic acid (DTPA) five,
Cupric sulfate pentahydrate, white oil D110, algae oil acid amides, Span-80, Tween-81, emulsifying dispersant OA90, azo, isomery hexadecane
Base APEO.
Further, each component content is calculated by weight as：
80 ~ 180 parts of acrylamide
50 ~ 100 parts of acrylic acid
50 ~ 180 parts of water
50 ~ 100 parts of liquid caustic soda
10 ~ 40 parts of 2- acrylamide-2-methylpro panesulfonic acids
0.002 ~ 0.008 part of methylene-bisacrylamide
HAS 20-50 parts
0.055 part of potassium bromate
0.140 part of sodium formate
0.800 part of five sodium of diethylene triamine pentacetic acid (DTPA)
0.020 part of cupric sulfate pentahydrate
150 ~ 260 parts of white oil D110
50 ~ 180 parts of algae oil acid amides
3 ~ 15 parts of Span-80
3 ~ 15 parts of Tween-81
2 ~ 10 parts of emulsifying dispersant OA90
0.180 part of azo
18 ~ 38 parts of isomery ceteth.
Further, the mass percentage concentration of the liquid caustic soda is 48%.
The preparation method of low-tension hydroxyl oximido emulsion flooding polymers, including：
By water, acrylamide, acrylic acid, liquid caustic soda sequentially adds 2- acrylamide-2-methylpro panesulfonic acids, and to be neutralized to pH pre-
If in scope, control whole process temperature is less than 50 degree, forms reaction solution；
By white oil D110, algae oil acid amides, Span-80, Tween-81, emulsifying dispersant OA90, azo sequentially add described
Dissolved completely in reaction solution, by potassium bromate, sodium formate, cupric sulfate pentahydrate suitable quantity of water, add the reaction solution；
With emulsifier to the mPas of viscosity 800 ~ 1200, nitrogen flushing 20 ~ 60 minutes, temperature control is at 10 ~ 20 degree, drop
The metabisulfite solution initiator for adding mass percentage concentration to be 1 ~ 3%, 43 degree are risen to by temperature with first rate；
Temperature stops that initiator is added dropwise after reaching 43 degree, when temperature is risen into temperature-resistant with the second speed, adds and triggers
Agent sees whether temperature changes, and reacts and terminates if temperature-resistant；
Reaction cools the temperature to 25 ~ 30 degree after terminating, add anti-phase dose, stirs 30 minutes with 100 mesh filter screen filtering and dischargings.
This is the product first step head product, then dissolves HAS, white oil D110 and emulsifier to just with suitable quantity of water
The corresponding viscosity of product, is stirred, while is warmed to 50 degree of insulation 3-5 hours, with 300 micron screen filtering and dischargings.
Further, the first rate is to rise 0.1 degree with 20 ~ 40 seconds.
Further, second speed is to rise 0.1 degree with 4 ~ 5 minutes.
Further, the algae oil acid amides extracts triglycerides by microalgae, liquid ammonia is added, in 1 Mpa, 150 degree of conditions
Lower reaction obtains for 10 hours.
Compared with prior art, low-tension hydroxyl oximido emulsion polymer provided by the invention has following advantage：
（1）The emulsion polymer filterable agent close to 1, advise by the polymer molecular structure for showing to obtain by emulsion copolymerization
It is whole, it is preferable closer to linear molecule, the homogeneity and mobility of solution.
（2）Dissolution velocity is fast, can be completely dissolved within 15~20 minutes, only the 1/4 of general polymer dissolution time, can be straight
The curing of row pipeline is tapped into, injection allocation apparatus is saved, simple flow, reduces surface construction investment.
（3）Emulsion polymer tackifying ability is strong, and 1000mg/L solution viscosities are higher than the general polymer of comparable sodium 14
Percentage point.
（4）Emulsion polymer stable performance（It is anti-shearing, ageing-resistant）, stable viscosity retention rate is higher than general polymer 15
Percentage point.
（5）Emulsion polymer has high-effective viscosity concurrently and reduces interface low-tension ability, not only improves raising fluidity control
Ability is advantageous to improve oil displacement efficiency again, therefore has preferable oil displacement efficiency.In polymer concentration 1000mg/L and 500mg/L
Under the conditions of, emulsion polymer system oil displacement efficiency is significantly better than the oil displacement efficiency of general polymer under same concentrations, respectively to carry more
High recovery rate 3.1 and 6 percentage points.Particularly emulsion polymer is under the conditions of concentration 500mg/L, the mg/L of comparable densities 1000
General polymer improves 2 percentage points of recovery ratio more.
In summary, there is low-tension hydroxyl oximido emulsion polymer provided by the invention unique structure design and emulsion to gather
Conjunction mode, recovery ratio can be both increased substantially, reduce polymer volume, ground investment can be reduced again, in, low-permeability oil
The exploitation in field is significant.
Embodiment
Below with reference to subordinate list and preferred embodiment, the present invention is further illustrated.
Embodiment one
The low-tension hydroxyl oximido emulsion flooding polymers that the present embodiment provides, it is composed of the following components：Acrylamide, propylene
Acid, water, liquid caustic soda, 2- acrylamide-2-methylpro panesulfonic acids, methylene-bisacrylamide, potassium bromate, sodium formate, divinyl three
The sodium of triamine pentaacetic acid five, cupric sulfate pentahydrate, white oil D110, algae oil acid amides, Span-80, Tween-81, emulsifying dispersant OA90, idol
Nitrogen, HAS, isomery ceteth.
Each component content is calculated by weight as：
80 ~ 180 parts of acrylamide
50 ~ 100 parts of acrylic acid
50 ~ 180 parts of water
50 ~ 100 parts of liquid caustic soda
10 ~ 40 parts of 2- acrylamide-2-methylpro panesulfonic acids
0.002 ~ 0.008 part of methylene-bisacrylamide
HAS 20-50 parts
0.055 part of potassium bromate
0.140 part of sodium formate
0.800 part of five sodium of diethylene triamine pentacetic acid (DTPA)
0.020 part of cupric sulfate pentahydrate
150 ~ 260 parts of white oil D110
50 ~ 180 parts of algae oil acid amides
3 ~ 15 parts of Span-80
3 ~ 15 parts of Tween-81
2 ~ 10 parts of emulsifying dispersant OA90
0.180 part of azo
18 ~ 38 parts of isomery ceteth.
In a preferable embodiment：Each component raw material is weighed by said components and proportioning：
80 ~ 180 kilograms of acrylamide
50 ~ double centner of acrylic acid
50 ~ 180 kilograms of water
50 ~ double centner of liquid caustic soda
10 ~ 40 kilograms of 2- acrylamide-2-methylpro panesulfonic acids
0.002 ~ 0.008 kilogram of methylene-bisacrylamide
20-50 kilograms of HAS
0.055 kilogram of potassium bromate
0.140 kilogram of sodium formate
0.800 kilogram of five sodium of diethylene triamine pentacetic acid (DTPA)
0.020 kilogram of cupric sulfate pentahydrate
150 ~ 260 kilograms of white oil D110
50 ~ 180 kilograms of algae oil acid amides
3 ~ 15 kilograms of Span-80
3 ~ 15 kilograms of Tween-81
2 ~ 10 kilograms of emulsifying dispersant OA90
0.180 kilogram of azo
18 ~ 38 kilograms of isomery ceteth.
In a preferable embodiment, the mass percentage concentration of the liquid caustic soda is 48%.
Low-tension hydroxyl oximido emulsion flooding polymers progressive provided by the invention can be tested, test result is as follows：
（1）The low-tension hydroxyl oximido emulsion displacement of reservoir oil of this implementation is gathered according to petrochina Polyacrylamides For Enhanced Oil Recoveries company standard
Compound has carried out the physicochemical property detection of sample.Test result shows the low-tension hydroxyl oximido emulsion flooding polymers body of this implementation
It is the high 12.5mPas of ratio of viscosities general polymer, and filterable agent is close to 1, illustrates the polymer closer to linear molecule,
Compound with regular structure, the homogeneity and mobility of solution are preferable；Meanwhile polymer dissolution velocity is very fast, can dissolve within 20 minutes
Entirely, only the 1/4 of general polymer dissolution time, can directly carry out pipeline curing.Specific test result such as table 1.
The polymer physicochemical property testing result of table 1
| Inspection project | Emulsion polymer | General polymer |
| Molecular weight（104） | 1558 | 1519 |
| Intrinsic viscosity（dL/g） | 20.9 | 20.5 |
| Degree of hydrolysis（mol%） | 25.2 | 25.0 |
| Viscosity（mPa·s） | 59.5 | 47.0 |
| Substance content（wt%） | 38.0 | 90.1 |
| Filterable agent | 1.1 | 1.3 |
| Water-insoluble（wt%） | 0.02 | 0.08 |
| Dissolution velocity（h） | ＜ 0.4 | ＜ 1.5 |
（2）Using the mg/L of normal saline solution compound concentration 5000 low-tension hydroxyl oximido emulsion flooding polymers mother liquor, dilution
To various concentrations point, determine each low-tension hydroxyl oximido emulsion flooding polymers and glue dense relation.As a result show, low of the present embodiment
Power hydroxyl oximido emulsion flooding polymers are respectively provided with preferable thickening property in various concentrations point, in the bar that concentration is 1000 mg/L
Under part, its system viscosity is higher than general polymer 14.2 percentage points.Specific comparing result is as shown in table 2.
The polymer viscosified performance comparison evaluation result of table 2
（3）Low-tension hydroxyl oximido emulsion flooding polymers mother liquor of the normal saline solution compound concentration for 5000 mg/L is used, then
The purpose liquid that concentration is 1000 mg/L is diluted to, measure polymer solution viscosity changes with time situation.As a result show, breast
Liquid polymer has higher viscosity retention ratio and viscosity retention, is placed 90 days under the conditions of 45 DEG C, emulsion polymer viscosity
Retention rate is higher than general polymer 15.2 percentage points 72.8%, illustrates in ageing process, emulsion polymer stability compared with
It is good, be advantageous to keep higher operating viscosity in Underground Long-term oil displacement process.Specific test result is as shown in table 3.
The stability evaluation result of table 3
（4）With the low-tension hydroxyl oximido emulsion flooding polymers solution that normal saline solution compound concentration is 1000 mg/L, use
Waring agitators shear 30s, solution viscosity before and after measure shearing with 5000 r/min speed.As a result show, emulsion polymerization
Viscosity retention ratio reaches 73.8% after the shearing of thing, higher than general polymer 13.7 percentage points, is advantageous to by injection allocation of ground
Device is sheared with after the shearing of stratum borehole, retains higher underground activities viscosity.Specific test result is as shown in table 4.
The cutting performance evaluation result of table 4
（5）Under the conditions of 45 DEG C, the low-tension hydroxyl oximido emulsion displacement of reservoir oil that measure concentration is 1000mg/L and 500mg/L polymerize
Interfacial tension between thing emulsion and dewatered oil.As a result show, the interfacial tension between emulsion polymer and crude oil with concentration raise and
Slightly diminish, interfacial tension is about a quarter of general polymer, illustrates the surface-active introduced in emulsion polymerization process
Material reduces interface tension force, is advantageous to improve the mobility and washing oil ability of solution.
The interfacial tension analysis result of table 5（Unit：mN/m）
（6）The low-tension hydroxyl oximido emulsion flooding polymers solution for being 1000mg/L with normal saline solution compound concentration, with
0.6mL/min speed injection rock core, it is poly- to terminate note when injecting pressure continuous and stable；Standard salt is injected with identical injection rate again
Water, injection pressure continuous and stable terminate to inject later.As a result show：Two kinds of polymer solution injects smoothly, and rock does not occur
Core clogging, and emulsion polymer resistance coefficient illustrates emulsion polymer in porous media flow apparently higher than general polymer
Tackifying ability is equally relatively strong during dynamic, is consistent with apparent viscosity test rule.Specific experiment result such as table 6.
The rock core-flowage experimental result of table 6（Homogeneous rock core, the cm of 10 cm × 2.5）
（7）Prepare low-tension hydroxyl oximido emulsion flooding polymers mother liquor and be diluted to the purpose liquid of various concentrations, with
0.6mL/min speed injects normal saline solution to physical model, terminates water drive when aqueous more than 98%；Injection of polymer solution
0.57PV and metaideophone normal saline solution, produce and terminate to test when liquid is aqueous to be more than more than 98%.It is dense in polymer from experimental result
Spend under the conditions of 1000mg/L and 500mg/L, emulsion polymer system oil displacement efficiency is significantly better than general polymer under same concentrations
Oil displacement efficiency, it is respectively to improve recovery ratios 3.1 and 6 percentage points more.Particularly emulsion polymer is in concentration 500mg/L conditions
Under, oil displacement efficiency is better than 1000 mg/L general polymers, can improve 2 percentage points of recovery ratio, and reduce polymer volume more
50%.Illustrate that tackifying ability and the reduction interfacial tension of emulsion polymer are stronger, be advantageous to increase the capillary number of oil displacement process, energy
The oil displacement efficiency of system is improved more significantly.Specific experiment result is as shown in table 7.
The oil displacement experiment result of table 7（Natural core, size are 10 cm, 2.5 cm）
Compared with prior art, displacement of reservoir oil low-tension hydroxyl oximido emulsion polymer of the invention has following advantage：
（1）The emulsion polymer filterable agent close to 1, advise by the polymer molecular structure for showing to obtain by emulsion copolymerization
It is whole, it is preferable closer to linear molecule, the homogeneity and mobility of solution.
（2）Dissolution velocity is fast, can be completely dissolved within 15~20 minutes, only the 1/4 of general polymer dissolution time, can be straight
The curing of row pipeline is tapped into, injection allocation apparatus is saved, simple flow, reduces surface construction investment.
（3）Emulsion polymer tackifying ability is strong, and 1000mg/L solution viscosities are higher than the general polymer of comparable sodium 14
Percentage point.
（4）Emulsion polymer stable performance（It is anti-shearing, ageing-resistant）, stable viscosity retention rate is higher than general polymer 15
Percentage point.
（5）Emulsion polymer has high-effective viscosity concurrently and reduces interfacial tension ability, not only improves and improves fluidity control energy
Power is advantageous to improve oil displacement efficiency again, therefore has preferable oil displacement efficiency.In polymer concentration 1000mg/L and 500mg/L bar
Under part, emulsion polymer system oil displacement efficiency is significantly better than the oil displacement efficiency of general polymer under same concentrations, respectively to improve more
Recovery ratio 3.1 and 6 percentage points.For particularly emulsion polymer under the conditions of concentration 500mg/L, the mg/L of comparable densities 1000 is general
Logical polymer improves 2 percentage points of recovery ratio more.
In summary, there is displacement of reservoir oil low-tension hydroxyl oximido emulsion polymer of the present invention unique structure design and emulsion to gather
Conjunction mode, you can increase substantially recovery ratio, reduce polymer volume, ground investment can be reduced again, in, low-permeability oil
The exploitation in field is significant.
Embodiment two
The preparation method for the low-tension hydroxyl oximido emulsion flooding polymers that the embodiment of the present invention two provides, including：
（1）By water, acrylamide, acrylic acid, liquid caustic soda sequentially adds 2- acrylamide-2-methylpro panesulfonic acids and is neutralized to pH
In preset range, control whole process temperature is less than 50 degree, forms reaction solution；
（2）By white oil D110, algae oil acid amides, span 80, sorbimacrogol oleate100, emulsifying dispersant OA90, azo sequentially add described
Dissolved completely in reaction solution, by potassium bromate, sodium formate, cupric sulfate pentahydrate suitable quantity of water, add the reaction solution；In this example, institute
State algae oil acid amides and triglycerides is extracted by microalgae, add liquid ammonia, react 10 hours and obtain under the conditions of 1 Mpa, 150 degree.（3）
With emulsifier to 800 ~ 1200mPas of viscosity, nitrogen flushing 20 ~ 60 minutes, quality percentage is added dropwise at 10 ~ 20 degree in temperature control
Concentration is 1 ~ 3% metabisulfite solution initiator, and temperature is risen into 43 degree with first rate；In this example, first speed
Rate is to rise 0.1 degree with 20 ~ 40 seconds.
（4）Temperature stops that initiator is added dropwise after reaching 43 degree, and when temperature is risen into temperature-resistant with the second speed, addition is drawn
Hair agent sees whether temperature changes, and reacts and terminates if temperature-resistant；In this example, second speed is to rise 0.1 with 4 ~ 5 minutes
Degree.
（5）Reaction cools the temperature to 25 ~ 30 degree after terminating, add anti-phase dose, and stirring is filtered out for 30 minutes with 100 mesh filter screens
Material.
（6）This is the product first step head product, then dissolves HAS, white oil D110 and emulsifier with suitable quantity of water
To the corresponding viscosity of head product, stirred, while be warmed to 50 degree of insulation 3-5 hours, with 300 micron screen mistakes
Filter out material.
Finally illustrate, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to compared with
The present invention is described in detail good embodiment, it will be understood by those within the art that, can be to the skill of the present invention
Art scheme is modified or equivalent substitution, and without departing from the objective and scope of technical solution of the present invention, it all should cover at this
Among the right of invention.
Claims (1)
1. a kind of low-tension hydroxyl oximido emulsion flooding polymers, it is characterised in that composed of the following components：Acrylamide, propylene
Acid, water, liquid caustic soda, 2- acrylamide-2-methylpro panesulfonic acids, methylene-bisacrylamide, potassium bromate, sodium formate, divinyl three
The sodium of triamine pentaacetic acid five, cupric sulfate pentahydrate, HAS, white oil D110, algae oil acid amides, Span-80, Tween-81, emulsion dispersion
Agent OA90, azo, isomery ceteth；
Each component content is calculated by weight as：
80 ~ 180 parts of acrylamide
50 ~ 100 parts of acrylic acid
50 ~ 180 parts of water
50 ~ 100 parts of liquid caustic soda
10 ~ 40 parts of 2- acrylamide-2-methylpro panesulfonic acids
The .008 parts of the .002 of methylene-bisacrylamide 0 ~ 0
HAS 20-50 parts
The .055 parts of potassium bromate 0
The .140 parts of sodium formate 0
The .800 parts of five sodium of diethylene triamine pentacetic acid (DTPA) 0
The .020 parts of cupric sulfate pentahydrate 0
150 ~ 260 parts of white oil D110
50 ~ 180 parts of algae oil acid amides
3 ~ 15 parts of Span-80
3 ~ 15 parts of Tween-81
2 ~ 10 parts of emulsifying dispersant OA90
The .180 parts of azo 0
18 ~ 38 parts of isomery ceteth；
The mass percentage concentration of the liquid caustic soda is 48%.
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