CN109679008A - A kind of displacement of reservoir oil ultra high molecular weight anion-type polyacrylamide and its preparation method and application - Google Patents
A kind of displacement of reservoir oil ultra high molecular weight anion-type polyacrylamide and its preparation method and application Download PDFInfo
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- CN109679008A CN109679008A CN201910032124.0A CN201910032124A CN109679008A CN 109679008 A CN109679008 A CN 109679008A CN 201910032124 A CN201910032124 A CN 201910032124A CN 109679008 A CN109679008 A CN 109679008A
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- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 238000006073 displacement reaction Methods 0.000 title claims abstract description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000084 colloidal system Substances 0.000 claims abstract description 16
- HRPVXLWXLXDGHG-UHFFFAOYSA-N acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 238000011084 recovery Methods 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 239000003638 reducing agent Substances 0.000 claims abstract description 11
- 239000003999 initiator 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 9
- 239000004280 Sodium formate Substances 0.000 claims abstract description 9
- ZGKNDXOLMOFEJH-UHFFFAOYSA-M Sodium hypophosphite Chemical compound [Na+].[O-]P=O ZGKNDXOLMOFEJH-UHFFFAOYSA-M 0.000 claims abstract description 9
- -1 chain regulator Substances 0.000 claims abstract description 9
- 235000019254 sodium formate Nutrition 0.000 claims abstract description 9
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 8
- 239000008139 complexing agent Substances 0.000 claims abstract description 8
- 230000003301 hydrolyzing Effects 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 150000001408 amides Chemical class 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- KCXVZYZYPLLWCC-UHFFFAOYSA-N edta Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 8
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 8
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 7
- 239000006184 cosolvent Substances 0.000 claims description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N Adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N Ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tBuOOH Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 6
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L Sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- IIACRCGMVDHOTQ-UHFFFAOYSA-N Sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001409 amidines Chemical class 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 230000001590 oxidative Effects 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N 1,2-ethanediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-Dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 3
- XRUKRHLZDVJJSX-UHFFFAOYSA-N 4-cyanopentanoic acid Chemical class N#CC(C)CCC(O)=O XRUKRHLZDVJJSX-UHFFFAOYSA-N 0.000 claims description 3
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Incidol Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L Potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- IKDDWMXNNQORQA-UHFFFAOYSA-N [Na].P(O)(O)=O Chemical compound [Na].P(O)(O)=O IKDDWMXNNQORQA-UHFFFAOYSA-N 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- SGSXYQPXIVHYON-UHFFFAOYSA-M azanium;iron;sulfate Chemical compound [NH4+].[Fe].[O-]S([O-])(=O)=O SGSXYQPXIVHYON-UHFFFAOYSA-M 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 3
- 239000001184 potassium carbonate Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 3
- KQJQICVXLJTWQD-UHFFFAOYSA-N N-methylthiourea Chemical compound CNC(N)=S KQJQICVXLJTWQD-UHFFFAOYSA-N 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 239000001187 sodium carbonate Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- OROQEEMZZJQQSA-UHFFFAOYSA-N [N].NC(=O)C=C Chemical compound [N].NC(=O)C=C OROQEEMZZJQQSA-UHFFFAOYSA-N 0.000 claims 1
- 230000000536 complexating Effects 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- 150000002829 nitrogen Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 61
- 239000003921 oil Substances 0.000 description 49
- 125000000129 anionic group Chemical group 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QHDRKFYEGYYIIK-UHFFFAOYSA-N 3-methylbutanenitrile Chemical compound CC(C)CC#N QHDRKFYEGYYIIK-UHFFFAOYSA-N 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L Iron(II) sulfate Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-N Peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- WJEIYVAPNMUNIU-UHFFFAOYSA-N [Na].OC(O)=O Chemical compound [Na].OC(O)=O WJEIYVAPNMUNIU-UHFFFAOYSA-N 0.000 description 1
- PMUIBVMKQVKHBE-UHFFFAOYSA-N [S].NC(N)=O Chemical group [S].NC(N)=O PMUIBVMKQVKHBE-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005039 chemical industry Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 125000004435 hydrogen atoms Chemical class [H]* 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 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
- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/52—Amides or imides
- C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F120/56—Acrylamide; Methacrylamide
-
- 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
-
- 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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/882—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The present invention relates to a kind of displacement of reservoir oil ultra high molecular weight anion-type polyacrylamides and its preparation method and application.Preparation method includes: that nitrogen is passed through into the solution comprising acrylamide, and azo-initiator, complexing agent, chain regulator, Oxidizing and Reducing Agents are successively added into solution, and polymerization obtains non-ionic polyacrylamide colloid；Chain regulator includes principal component and auxiliary element, and principal component includes sodium formate, and auxiliary element includes sodium hypophosphite, and the mass ratio of principal component and auxiliary element is (10~18): 1；Non-ionic amide colloid is crushed, hydrolytic reagent is added and is hydrolyzed, obtains displacement of reservoir oil ultra high molecular weight anion-type polyacrylamide.Using the glutinous equal relative molecular mass of anion-polyacrylamide made from this method 30,000,000 or more, water insoluble matter content≤0.2% is used as oil displacement agent in tertiary oil production in oil field, and oil displacement efficiency is higher, and oil recovery factor can be improved 18~29%.
Description
Technical field
The present invention relates to super high molecular weight polymer technical field more particularly to a kind of displacement of reservoir oil ultra-high-molecular aniouics
Type polyacrylamide and its preparation method and application.
Background technique
Polyacrylamide (PAM) is a kind of water soluble polymer, and there are amide groups active groups in molecular structure
Group, easily by being grafted or being crosslinked to obtain a variety of modifiers of branch or reticular structure.PAM molecule can introduce various ionic groups
To obtain specific performance, it is widely used in the every field such as chemical industry, metallurgy, geology, coal, petroleum, papermaking and water process,
Title with " all trades auxiliary agent ", it is especially maximum with oilfield exploitation dosage.Lot of domestic and international oil field with exploitation continuous progress,
Tertiary phase is much come into.Enough crude oil can not be produced by water filling or gas injection etc., cost for oil production is held
Continue high.The tertiary oil recovery i.e. injection of polymer into oil well substantially reduces the oil water interfacial tension near oil reservoir and increases injection
The viscosity and elasticity of water, so that reducing grease velocity ratio expands oil reservoir both macro and micro sweep efficiency, further displacement water drive is residual
Remaining oil saturation is greatly lowered in excess oil, to achieve the purpose that improve oil recovery factor.
Flooding polymers are most widely used with anion-polyacrylamide, and oil displacement efficiency is best.Oil reservoir environment is complicated, high
Temperature is with high salt, this requires polymer performance very high.The maximum existing polyacrylamide polymers for oil displacement product dosage in market is super
High molecular weight polyacrylamide and the polyacrylamide of the monomer containing temperature-resistant and anti-salt type etc..Super high molecular weight polyacrylamide molecular weight
Mainly between 2500~30,000,000, only a few is between 3000~33,000,000, and this kind of polyacrylamides are in salt water and high temperature
Strand curling can occur for environment, and solution viscosity is made to decline to a great extent, and oil displacement efficiency decline is serious, and water-soluble is poor, shadow
Ring using effect；The polyacrylamide of the monomer containing temperature-resistant and anti-salt type is due to temperature-resistant anti-salt monomer higher cost, and after copolymerization
Molecular weight is lower, can only be used for specific occasion on a small quantity, can not large-scale application in displacement of reservoir oil field.
In view of this, the present invention is specifically proposed.
Summary of the invention
The object of the present invention is to provide it is a kind of it is at low cost, (30,000,000 or more, optimal technical scheme can reach molecular weight superelevation
35000000 or more) it, good displacement of reservoir oil novel super-high molecular weight anionic type polyacrylamide of dissolubility and preparation method thereof and answers
With to solve the problems, such as present in existing displacement of reservoir oil anion-polyacrylamide one or more.
To achieve the goals above, the present invention provides the following technical scheme that
1, a kind of preparation method of displacement of reservoir oil ultra high molecular weight anion-type polyacrylamide, includes the following steps:
(1) it is passed through nitrogen into the solution comprising acrylamide, azo-initiator, network are then successively added into solution
Mixture, chain regulator, Oxidizing and Reducing Agents, polymerization, obtain non-ionic polyacrylamide colloid；Wherein, the chain is adjusted
Agent includes principal component and auxiliary element, and the principal component includes sodium formate, and the auxiliary element includes sodium hypophosphite, principal component
Mass ratio with auxiliary element is (10~18): 1；
(2) non-ionic amide colloid is crushed, be added hydrolytic reagent be hydrolyzed, obtain displacement of reservoir oil super high molecular weight yin from
Subtype polyacrylamide.
2, the mass ratio of preparation method according to technical solution 1, the principal component and the auxiliary element be (12~
15): 1.
3, preparation method according to technical solution 1, the auxiliary element also include lauryl mercaptan and/or sulfurous
Sour hydrogen sodium.
4, according to the described in any item preparation methods of technical solution 1 to 3, the quality of the chain regulator is the solution matter
The 0.0015%~0.0032% of amount.
5, preparation method according to technical solution 1, the quality of the chain regulator are the solution quality
0.0018%~0.0026%.
6, preparation method according to technical solution 1, also includes cosolvent in the solution, and the cosolvent is selected from sulphur
Urea, urea, acetamide are any one or more of, and quality accounts for the 0.5%~2.3% of the solution quality；And/or
The acrylamide volume quality accounts for the 16~30% of the solution quality, preferably 17~23%.
7, the preparation method according to technical solution 6, the quality of the cosolvent account for the solution quality 0.8%~
1%.
8, the preparation method according to technical solution 6, the quality of the acrylamide account for the solution quality 17~
23%.
9, preparation method according to technical solution 1, the azo-initiator are selected from azodiisobutyronitrile, azo two
The double 4- cyanopentanoic acids of isobutyl cyanide, azo diisobutyl amidine hydrochloride, 4,4 '-azos are any one or more of, and quality is described
The 0.0015%~0.0035% of solution quality,；
The complexing agent is selected from disodium ethylene diamine tetraacetate, ethylene diamine tetra methylene phosphonic acid sodium, ethylenediamine tetra-acetic acid, substitute alkali
Any one or more of, quality is the 0.0002%~0.0008% of the solution quality；
The oxidant is selected from dibenzoyl peroxide, ammonium persulfate, tert-butyl hydroperoxide, potassium peroxydisulfate, persulfuric acid
Sodium is any one or more of, and quality is the 0.00006%~0.00018% of the solution quality；And/or
Any of the reducing agent in sodium hydrogensulfite, sodium pyrosulfite, iron ammonium sulfate, green vitriol
Kind is a variety of, and quality is the 0.00005%~0.00015% of the solution quality.
10, the preparation method according to technical solution 9, the quality of the azo-initiator are the solution quality
0.002%~0.0026%.
11, the preparation method according to technical solution 9, the quality of the complexing agent are the solution quality
0.0003%~0.0005%.
12, the preparation method according to technical solution 9, the quality of the oxidant are the solution quality
0.00008%~0.00015%.
13, the preparation method according to technical solution 9, the quality of the reducing agent are the solution quality
0.00006%~0.0001%.
14, preparation method according to technical solution 1, the hydrolytic reagent are selected from sodium hydroxide, potassium hydroxide, carbonic acid
Sodium, potassium carbonate are any one or more of, and quality is the 2.8%~5.0% of the quality of the non-ionic polyacrylamide colloid.
15, the preparation method according to technical solution 14, the quality of the hydrolytic reagent are the 3.5% of the solution quality
~3.9%.
16, preparation method according to technical solution 1 is also wrapped before being passed through nitrogen into the solution comprising acrylamide
Include following steps: using sulfamic acid, adipic acid, any one or more of component of acetic acid by the solution comprising acrylamide
PH is adjusted to 7.2~7.5.
17, preparation method according to technical solution 1 sequentially adds azo at 1~3 DEG C and draws in step (1)
Send out agent, complexing agent, chain regulator, Oxidizing and Reducing Agents；
In step (1), the time for leading to nitrogen is 40~60min；
In step (1), the time of polymerization is 3~6h；And/or
In step (2), hydrolysis carries out 3~5h at 80~90 DEG C.
18, a kind of displacement of reservoir oil ultra high molecular weight anion-type polyacrylamide, using any one of technical solution 1 to 17 institute
It states preparation method to be made, it is preferable that the anion-polyacrylamide has the property that
Sticking equal relative molecular mass is 3900~41,000,000 and/or water insoluble matter content≤0.2%.
19, the displacement of reservoir oil described in technical solution 18 uses ultra high molecular weight anion-type polyacrylamide as oil displacement agent in oil field
Application in tertiary oil recovery.
Beneficial effect
Above-mentioned technical proposal of the invention has the advantages that
The method of the present invention stable preparation process, reaction time is short, at low cost, high production efficiency, is suitble to industrialized production；This
The obtained novel super-high molecular weight anionic type polyacrylamide content of monomer of invention is few, water-soluble is good, molecular weight superelevation,
Its molecular weight is more than molecular weight 700~10,000,000 of market routine displacement of reservoir oil superelevation anion-polyacrylamide product.
Other class displacement of reservoir oil ultra high molecular weight anion-type polyacrylamides are compared, using the novel super-high in the present invention point
Sub- weight anion-type polyacrylamide can effectively improve oil displacement efficiency and original as the application of oil displacement agent in tertiary oil production in oil field
Oil recovery 18~29%.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this hair
Bright technical solution is clearly and completely described.Obviously, described embodiment is a part of the embodiments of the present invention, and
The embodiment being not all of.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work
Under the premise of every other embodiment obtained, shall fall within the protection scope of the present invention.
The present invention provides a kind of preparation method of displacement of reservoir oil ultra high molecular weight anion-type polyacrylamide, the preparations
Method includes the following steps:
(1) it is passed through nitrogen into the solution comprising acrylamide, azo-initiator, network are then successively added into solution
Mixture, chain regulator, Oxidizing and Reducing Agents, polymerization, obtain non-ionic polyacrylamide colloid；Wherein, the chain is adjusted
Agent includes principal component and auxiliary element, and the principal component includes sodium formate, and the auxiliary element includes sodium hypophosphite, principal component
Mass ratio with auxiliary element is (10~18): 1, more preferably (12~15): 1；
(2) non-ionic amide colloid is crushed, be added hydrolytic reagent be hydrolyzed, obtain displacement of reservoir oil super high molecular weight yin from
Subtype polyacrylamide.
In preparation method provided by the invention, the principal component and auxiliary element in chain regulator are mixed according to specific proportion
It closes and uses, sodium formate can increase substantially the molecular weight of polyacrylamide, compared with the polyacrylamide of other chain regulators synthesis
Molecular weight is obviously higher, but polyacrylamide course of dissolution prepared by only with sodium formate as chain regulator when is slower, water-soluble
Solution property is poor.After sodium hypophosphite is added, polyacrylamide dissolution time obtained is short (being less than 1h).So the present invention uses first
Sour sodium is decided regulator, and sodium hypophosphite does auxiliary chain regulator, and gained Molecular Weight for Polyacrylamide uses more merely sodium formate institute
It is slightly lower to obtain Molecular Weight for Polyacrylamide, but water-soluble obviously improves, relatively the dissolution of the polyacrylamide obtained by sodium hypophosphite merely
Property is slightly worse, but molecular weight obviously becomes larger.
In some embodiments, the auxiliary element also includes lauryl mercaptan and/or sodium hydrogensulfite.
In some embodiments, the quality of the chain regulator be the solution quality 0.0015%~
0.0032%, for example, can be 0.0015%, 0.0020%, 0.0025%, 0.0030%, 0.0032%, preferably
0.0018%~0.0026%.
It in some embodiments, also include cosolvent in the solution, the cosolvent is selected from thiocarbamide, urea, acetyl
Amine is any one or more of, and quality accounts for the 0.5%~2.3% of the solution quality, for example, can for 0.5%, 1.0%,
1.5%, 2.0%, 2.3%, preferably 0.8%~1%.
In some embodiments, the quality of the acrylamide accounts for the 16~30% of the solution quality, for example, can
Think 16%, 17%, 18%, 19%, 20%, 25%, 30%, preferably 17~23%.
In some embodiments, the azo-initiator is selected from azodiisobutyronitrile, azobisisovaleronitrile, azo two
Isobutyl amidine hydrochloride, 4, the double 4- cyanopentanoic acids of 4 '-azos are any one or more of, and quality is the solution quality
0.0015%~0.0035%, for example, can be 0.0015%, 0.0020%, 0.0025%, 0.0030%, 0.0035%,
Preferably 0.002%~0.0026%.
In some embodiments, the complexing agent is selected from disodium ethylene diamine tetraacetate, ethylene diamine tetra methylene phosphonic acid sodium, second
Ethylenediamine tetraacetic acid (EDTA), substitute alkali are any one or more of, and quality is the 0.0002%~0.0008% of the solution quality, example
It such as, can be 0.0002%, 0.0003%, 0.0004%, 0.0005%, 0.0006%, 0.0007%, 0.0008%, preferably
It is 0.0003%~0.0005%.
In some embodiments, the oxidant is selected from dibenzoyl peroxide, ammonium persulfate, tert-butyl hydroperoxide
Hydrogen, potassium peroxydisulfate, sodium peroxydisulfate are any one or more of, quality be the solution quality 0.00006%~
0.00018%, for example, can for 0.00006%, 0.00007%, 0.00008%, 0.00009%, 0.00010%,
0.00011%, 0.00012%, 0.00015%, 0.00016%, 0.00018%, preferably 0.00008%~
0.00015%.
In some embodiments, the reducing agent is selected from sodium hydrogensulfite, sodium pyrosulfite, iron ammonium sulfate, seven water
Close that ferrous sulfate is any one or more of, quality is the 0.00005%~0.00015% of the solution quality, for example, can be with
For 0.00005%, 0.00006%, 0.00007%, 0.00008%, 0.00009%, 0.00010%, 0.00011%,
0.00012%, 0.00015%, preferably 0.00006%~0.0001%.
In some embodiments, the hydrolytic reagent appointing in sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate
One or more, quality is the 2.8%~5.0% of the quality of the non-ionic polyacrylamide colloid, for example, can be
2.8%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, preferably 3.5%~3.9%.
In some embodiments, further include following steps before nitrogen is passed through into the solution comprising acrylamide: adopting
The pH of the solution comprising acrylamide is adjusted to 7.2 with sulfamic acid, adipic acid, any one or more of component of acetic acid~
7.5。
In some embodiments, in step (1), azo-initiator, complexing agent, chain are sequentially added at 1~3 DEG C
Regulator, Oxidizing and Reducing Agents；
In step (1), the time for leading to nitrogen is 40~60min；
In step (1), the time of polymerization is 3~6h；And/or
In step (2), hydrolysis carries out 3~5h at 80~90 DEG C.
The present invention also provides a kind of displacement of reservoir oil ultra high molecular weight anion-type polyacrylamide, the anionic polypropylene
Amide is made using the preparation method provided by the invention, in preferred technical solution, the anionic polyacrylamide
Amine has the property that
Sticking equal relative molecular mass is 3900~41,000,000 and/or water insoluble matter content≤0.2%.
This displacement of reservoir oil provided by the invention uses ultra high molecular weight anion-type polyacrylamide as oil displacement agent in oil field three
Application in secondary oil recovery.
It is the embodiment that the present invention enumerates below.
Embodiment 1
(1) acrylamide and urea (urea is cosolvent) are thoroughly mixed uniformly with deionized water, are obtained total single
The mass percent concentration of the mixed liquor that the weight percent concentration of body acrylamide is 20%, the urea in mixed liquor is
0.8%, 7.2 are adjusted to the pH that sulfamic acid adjusts the mixed liquor, then with refrigeration equipment by the temperature of the mixed liquor
It is down to 1 DEG C.
(2) when the temperature of mixed liquor is down to 1 DEG C, the mixed liquor is moved into adiabatic reaction kettle, is inserted into temperature digital display
Meter, be passed through high pure nitrogen 40min thereto to remove the oxygen in mixed liquor, then sequentially added into the mixed liquor account for it is mixed
Close the ethylenediamine tetra-acetic acid of the azo diisobutyl amidine hydrochloride of the quality 0.002% of liquid, the quality 0.0003% for accounting for mixed liquor
Disodium, account for mixed liquor quality 0.0018% sodium formate and account for mixed liquor quality 0.00015% sodium hypophosphite, account for it is mixed
It closes the t-butyl hydroperoxide of the quality 0.00008% of liquid and accounts for 0.00006% green vitriol of quality of mixed liquor,
The viscosity of liquid to be mixed becomes larger, nitrogen is bubbled, and stops inflated with nitrogen, and closed adiabatic reaction kettle observes and records temperature change, continues
3h is reacted, the non-ionic polyacrylamide colloid of colloidal is obtained.
(3) the non-ionic polyacrylamide colloid of obtained colloidal is broken into the fritter of 3~5mm, is added to water
3.5% sodium hydroxide of dispergation weight is sufficiently mixed, and is put into thermostatic drying chamber, and 80 DEG C of temperature, the time continues 3h, is obtained new
Type ultra high molecular weight anion-type polyacrylamide colloid.
(4) displacement of reservoir oil with novel super-high molecular weight anionic type polyacrylamide colloid successively through granulation, drying and
The displacement of reservoir oil novel super-high molecular weight anionic type polyacrylamide of dry powder-shaped is made in the step of crushing.
That the preparation method is the same as that of Example 1 is substantially the same to embodiment 7 for embodiment 2, and difference is shown in Table 1.
The glutinous equal relative molecular mass and insolubles content of product made from embodiment 1 to embodiment 7 are measured, surveyed
Method for testing can carry out as follows:
(1) it sticks the measurement of equal relative molecular mass: measuring NaCl solution respectively by Ubbelohde viscometer and 0.1% (quality is dense
Degree is denoted as t for the delivery time of 0.1%) sample solution respectively0And t1, by following formula scales at sticking equal relative molecular mass:
In formula, the solid content of A- sample, the quality of m- sample,Average molecular weight, η sp=η r-1, η r=t1/t0,
[η]-inherent viscosity.
(2) measurement of insolubles content: weighing 2.0g sample, be accurate to 0.0002g, is slowly added into the Sheng stirred
In the beaker for having 1998.0g deionized water, whirlpool depth about 2cm is kept, until (time is about 1 hour) is completed in dissolution.Filtering
Solution weighs stainless with tap water natural flushing to insoluble matter as it can be seen that as far as possible flowing to end the liquid solution on stainless (steel) wire
The quality of steel mesh and insoluble matter colloid.
, in formula, w1- insolubles content is with mass fraction, m0Gross mass (total matter of deionized water and dry powder of-sample
Amount), m1The quality of-stainless (steel) wire, m2The gross mass of-stainless (steel) wire and insoluble matter.
(3) measurement of oil recovery factor: oil recovery factor refers in a certain economic limit, in modern engineering technology condition
Under, the percentage for the petroleum reserves that can be produced from oil reservoir original oil in place, its calculation formula is:
In formula, A- oil recovery factor is with mass fraction, V0The original geology storage capacity of-oil reservoir, V1- crude oil produced quantity.
Test result is shown in Table 1.
Embodiment 4 is in the preparation only with sodium formate as chain regulator.From test result as can be seen that in chain regulator
Dosage in the identical situation of embodiment 1, the production of the glutinous equal relative molecular mass of product made from embodiment 4 compared with embodiment 1
Product are slightly higher, but its dissolubility is poor, insolubles content height (up to 1.61%, be 16 times of embodiment 1), thus oil recovery factor is not
And embodiment 1.
Embodiment 5 is in the preparation only with sodium hypophosphite as chain regulator.From test result as can be seen that in chain tune
The dosage of agent is saved in the identical situation of embodiment 1, product dissolubility made from embodiment 5 is preferable, but sticks equal average molecular matter
Measure product much not as good as embodiment 1, stick equal relative molecular mass 30,000,000 hereinafter, influence to oil recovery factor also compared with
Greatly.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. a kind of preparation method of displacement of reservoir oil ultra high molecular weight anion-type polyacrylamide, which is characterized in that including walking as follows
It is rapid:
(1) it is passed through nitrogen into the solution comprising acrylamide, azo-initiator, complexing are then successively added into solution
Agent, chain regulator, Oxidizing and Reducing Agents, polymerization, obtain non-ionic polyacrylamide colloid；Wherein, the chain regulator
Comprising principal component and auxiliary element, the principal component include sodium formate, the auxiliary element include sodium hypophosphite, principal component and
The mass ratio of auxiliary element is (10~18): 1, more preferably (12~15): 1；
(2) non-ionic amide colloid is crushed, hydrolytic reagent is added and is hydrolyzed, obtains displacement of reservoir oil ultra high molecular weight anion-type
Polyacrylamide.
2. preparation method according to claim 1, which is characterized in that the auxiliary element also includes lauryl mercaptan
And/or sodium hydrogensulfite.
3. preparation method according to claim 1 or 2, which is characterized in that the quality of the chain regulator is the solution
The 0.0015%~0.0032% of quality, preferably 0.0018%~0.0026%.
4. preparation method according to claim 1, which is characterized in that also include cosolvent, the hydrotropy in the solution
Agent is any one or more of selected from thiocarbamide, urea, acetamide, and quality accounts for the 0.5%~2.3% of the solution quality, preferably
It is 0.8%~1%；And/or
The acrylamide volume quality accounts for the 16~30% of the solution quality, preferably 17~23%.
5. preparation method according to claim 1, which is characterized in that the azo-initiator is selected from two isobutyl of azo
The double 4- cyanopentanoic acids of nitrile, azobisisovaleronitrile, azo diisobutyl amidine hydrochloride, 4,4 '-azos are any one or more of, matter
Amount is the 0.0015%~0.0035% of the solution quality, preferably 0.002%~0.0026%；
The complexing agent is in disodium ethylene diamine tetraacetate, ethylene diamine tetra methylene phosphonic acid sodium, ethylenediamine tetra-acetic acid, substitute alkali
Any one or more, quality is the 0.0002%~0.0008% of the solution quality, preferably 0.0003%~0.0005%；
The oxidant is in dibenzoyl peroxide, ammonium persulfate, tert-butyl hydroperoxide, potassium peroxydisulfate, sodium peroxydisulfate
It is any one or more, quality be the solution quality 0.00006%~0.00018%, preferably 0.00008%~
0.00015%；And/or
The reducing agent be selected from any one of sodium hydrogensulfite, sodium pyrosulfite, iron ammonium sulfate, green vitriol or
A variety of, quality is the 0.00005%~0.00015% of the solution quality, preferably 0.00006%~0.0001%.
6. preparation method according to claim 1, which is characterized in that the hydrolytic reagent be selected from sodium hydroxide, potassium hydroxide,
Sodium carbonate, potassium carbonate are any one or more of, quality be the non-ionic polyacrylamide colloid quality 2.8%~
5.0%, preferably 3.5%~3.9%.
7. preparation method according to claim 1, which is characterized in that be passed through into the solution comprising acrylamide nitrogen it
Before further include following steps: acrylamide will be included using sulfamic acid, adipic acid, any one or more of component of acetic acid
The pH of solution is adjusted to 7.2~7.5.
8. preparation method according to claim 1, which is characterized in that in step (1), sequentially add idol at 1~3 DEG C
Nitrogen class initiator, complexing agent, chain regulator, Oxidizing and Reducing Agents；
In step (1), the time for leading to nitrogen is 40~60min；
In step (1), the time of polymerization is 3~6h；And/or
In step (2), hydrolysis carries out 3~5h at 80~90 DEG C.
9. a kind of displacement of reservoir oil ultra high molecular weight anion-type polyacrylamide, which is characterized in that any using claim 1 to 8
The item preparation method is made, it is preferable that the anion-polyacrylamide has the property that
Sticking equal relative molecular mass is 3900~41,000,000 and/or water insoluble matter content≤0.2%.
10. the displacement of reservoir oil as claimed in claim 9 use ultra high molecular weight anion-type polyacrylamide as oil displacement agent oil field three times
Application in oil recovery.
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| US6753388B1 (en) * | 2000-06-29 | 2004-06-22 | Nalco Company | Structurally-modified polymer flocculants |
| CN102372807A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Preparation method of heat-resistance and salt-tolerance anionic polyacrylamide for oil displacement |
| CN103509146A (en) * | 2012-06-27 | 2014-01-15 | 中国石油化工股份有限公司 | Preparation method of ultra-high molecular weight anionic polyacrylamide |
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