CN1247735C - Ternary polymer oil-displacing agent, and its preparing method and use - Google Patents
Ternary polymer oil-displacing agent, and its preparing method and use Download PDFInfo
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- CN1247735C CN1247735C CN 200310101796 CN200310101796A CN1247735C CN 1247735 C CN1247735 C CN 1247735C CN 200310101796 CN200310101796 CN 200310101796 CN 200310101796 A CN200310101796 A CN 200310101796A CN 1247735 C CN1247735 C CN 1247735C
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- 229920000642 polymer Polymers 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 13
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 12
- OHXAOPZTJOUYKM-UHFFFAOYSA-N 3-Chloro-2-methylpropene Chemical compound CC(=C)CCl OHXAOPZTJOUYKM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000011084 recovery Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- JPAOMENBKRZQDR-UHFFFAOYSA-N CC=CC.[Na] Chemical compound CC=CC.[Na] JPAOMENBKRZQDR-UHFFFAOYSA-N 0.000 claims description 20
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000004159 Potassium persulphate Substances 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 7
- 235000019394 potassium persulphate Nutrition 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 230000001143 conditioned effect Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 230000001939 inductive effect Effects 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 abstract description 6
- 235000010265 sodium sulphite Nutrition 0.000 abstract description 3
- 229920001897 terpolymer Polymers 0.000 abstract 4
- AIDWMELCBZUXNK-UHFFFAOYSA-M sodium;but-2-ene-1-sulfonate Chemical compound [Na+].CC=CCS([O-])(=O)=O AIDWMELCBZUXNK-UHFFFAOYSA-M 0.000 abstract 2
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 abstract 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000000243 solution Substances 0.000 description 20
- 238000006460 hydrolysis reaction Methods 0.000 description 17
- 230000007062 hydrolysis Effects 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 10
- 229920002401 polyacrylamide Polymers 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- -1 polypropylene Polymers 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000004088 simulation Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- KYQODXQIAJFKPH-UHFFFAOYSA-N diazanium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [NH4+].[NH4+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O KYQODXQIAJFKPH-UHFFFAOYSA-N 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005065 mining Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 230000033558 biomineral tissue development Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000013054 paper strength agent Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention discloses a terpolymer oil displacing agent and a preparation method and the application thereof. A polymer is obtained by the polymerization of three components of a) 60 wt% to 99.96 wt% of acrylamide, b) 0.006 wt% to 25 wt% of sodium methyl allyl sulfonate and c) 0.01 wt% to 15 wt% of N, N-dimethyl acrylamide. Weight percentage is measured according to the total weight of added monomers. The weight content of sulfonic groups of the polymer is from 0.5 to 22.7%, wherein the (b) component of sodium methyl allyl sulfonate is obtained by the reaction of methylallyl chloride and sodium sulfite, and a reactive pH value is controlled between 8.5 and 10.0. The terpolymer oil displacing agent is adopted, and the temperature resistance and the salt resistance of the terpolymer oil displacing agent in an oil recovery process can be effectively enhanced. The terpolymer oil displacing agent has wide economic benefit.
Description
Technical field
The present invention relates to a kind of water-soluble high-molecular material, specifically, relate to a kind of ter-polymers oil-displacing agent and its production and application.
Background technology
Polymer flooding is the big class of one in the chemical displacement of reservoir oil, in tertiary oil recovery technology, adopts polymer flooding can increase substantially oil recovery rate, obtains great economic benefit and social benefit.
At present, most widely used polymer oil-displacing agent is the synthetic polymer oil-displacing agent based on polyacrylamide, as the polyacrylamide of partial hydrolysis, polyacrylic acid sodium salt etc., this oil-displacing agent is obtained by the acrylamide homopolymerization, have stronger tackifying ability, but exist the problem of heatproof, anti-salt property, under reservoir condition, structure properties instability, solution viscosity descend significantly along with the increase of temperature and salinity.Compare with ground, the polymer solution viscosity loss of injecting the stratum is a lot, can reduce 60-70%, has a strong impact on oil displacement efficiency.
Chinese patent CN1084339C and CN1022758C disclose a kind of polymkeric substance and synthetic method thereof of partial hydrolysis acrylamide.The polyacrylamide that this method obtains lacks the temperature resistant antisalt performance, and therefore under high temperature and high salinity condition, soltion viscosity can descend a lot, does not have enough oil-displacement capacities.
CN1105417A discloses a kind of cross-linked polymer oil-displacing agent and compound method thereof, and polymkeric substance mainly is polyacrylamide or xanthan gum, and linking agent mainly is a Chromic lactate; In the process of injection of polymer solution, add linking agent, make polymers soln tackify in the flow process in the stratum, improved oil displacement efficiency.But this method is the effect that produces tackify by crosslinking reaction, does not relate to the technology and the performance of anti-salt temperature-resistant.
CN1074019C discloses a kind of preparation method of polymer oil-displacing agent, be characterized in the compound preparation polymer oil-displacing agent of two or more polymer interchain molecules by complementary structure, this method requires to prepare respectively multiple acrylamide polymer, make it compound preparation then, its purpose also is in order to increase the viscosity of acrylamide polymer solution, not relate to the technology that keeps viscosity under high temperature and high salinity reservoir condition.
CN86104196A discloses the polymkeric substance and the synthetic method thereof of a kind of N-of containing (2-hydroxyl-3-sulfonic acid propyl group) acid amides, and this method can be used to synthetic various types ofly contain sulfonicly, contains the water-soluble polymers of other functional group simultaneously.What but this patent adopted is macromolecule modified method, makes by making acrylamide polymer and the replacement amine generation amide group shift reaction that contains sulfonic chemically reactive substance.Because high molecular modified-reaction degree is often very limited, therefore, the sulfonic group polymkeric substance that contains that produces does not have enough heatproofs and anti-salt property.
CN1064375C discloses a kind of acrylamide polymer.As paper strength agents, need the molecular weight height of this acrylamide polymer, but the viscosity of its aqueous solution under high density is very low.Only the Bu Luoke Field viscosity of this acrylamide polymer aqueous solution under 25 ℃ is limited in its specification sheets, do not point out that this polymkeric substance has in high salinity and following ability that can keep viscosity of hot conditions, and the disclosed technical scheme of this patent is not a purpose to keep enough viscosity under high salinity and high-temperature oil reservoir condition also.
In sum, oil-displacing agent of the prior art exists heatproof, the insufficient problem of anti-salt property, therefore, need propose a kind of polymer oil-displacing agent with temperature resistant antisalt performance at the deficiency of prior art existence.
Summary of the invention
One of purpose of the present invention is to propose a kind of polymer oil-displacing agent with temperature resistant antisalt performance.
Two of purpose of the present invention provides the preparation method of polymer oil-displacing agent of the present invention.
Three of purpose of the present invention provides the application of polymer oil-displacing agent of the present invention.
The inventor has carried out extensive studies to polymer oil-displacing agent, finds to introduce in polymkeric substance to contain sulfonic group monomer, huge functional modification methods such as side group monomer, can effectively improve polymkeric substance temperature resistance salt resistant character.
One of purpose of the present invention is achieved in that
1. directly since three kinds of monomer preparations, polymer performance is substantially improved;
2. in a cover reaction unit, polystep reactions such as polymerization, crosslinked, hydrolysis are carried out simultaneously, have polymerization, the crosslinked and multiple reactive mode of hydrolysis simultaneously, can utilize the difference of its level of response respectively, realize selection and adjustment heatproof and anti-salt property.
Concrete, ter-polymers oil-displacing agent of the present invention comprises the polymkeric substance that is obtained through polyreaction by following component: by the adding total monomer weight,
A) acrylamide of 60%-99.96% (weight);
B) methylpropene sodium sulfonate of 0.006%-25% (weight);
C) N,N-DMAA of 0.01%-15% (weight);
The content of the sulfonic acid group of this polymkeric substance is 0.5-22.7% (weight), and described (b) component methylpropene sodium sulfonate is that the pH value of the reaction that obtained by the reaction of methylallyl chloride and S-WAT is controlled at 8.5-10.0, and the preferred reaction pH value is 9.0-9.8.The main 2 θ values of the X RD of Zhi Bei methylpropene sodium sulfonate are respectively with this understanding: 7.04; 28.44; 35.76.
The sulfonic group weight content of polymkeric substance of the present invention is that the element sulphur cubage by analyses obtains.
The methylpropene sodium sulfonate that the present invention uses is a kind of sulfonic vinyl monomer that contains, after polymerization, and the sulfonic acid group (SO on the macromolecular chain
3 -) carboxyl (COO that produces with the amide moieties hydrolysis
-Base) synergy is borrowed its good hydration and steric effect, hinders positive ion and enters-COO
-The base the aquation territory and reduce-COO
-Base is to the susceptibility of salt, SO in addition
3 -Hydratability much larger than-COO
-Hydratability.Therefore, temperature influence is less, so can improve its temperature resistant antisalt ability.
Described polyreaction adds polynary initiator polymerization by adding total monomer weight, and used initiator is persulphate 0.0005%-0.007% (weight); Sodium bisulfite 0.00003%-0.0005% (weight); Methacrylic acid N, N-dimethylaminoethyl (DMAEMA) 0.0002%-0.006% (weight).
Wherein persulphate comprises Potassium Persulphate, Sodium Persulfate and ammonium persulphate.
Described polymkeric substance obtains through solution polymerization, and monomeric gross weight is the 10-45% of weight of solvent.
Described polymerization reaction time is 2-20 hour, and pH is 5-11.5, makes the degree of hydrolysis of polymkeric substance be controlled at 5-25%.
The preparation method of ter-polymers oil-displacing agent of the present invention may further comprise the steps:
(1) preparation methylpropene sodium sulfonate
Being mixed in the aqueous solution by methylallyl chloride and S-WAT, is 30～70 ℃ of reactions down in temperature, and pH value is controlled at 8.5-10.0.
(2) preparation of ter-polymers
The acrylamide, the N that in polymeric kettle, add required weight, N-DMAA and homemade methylpropene sodium sulfonate, making total monomer weight with the deionized water adjusting is the 10-45% of weight of solvent, the pH value of conditioned reaction liquid is 5-11.5, feed nitrogen down at starting temperature 15-70 ℃, the aqueous solution that adds Potassium Persulphate and S-WAT, add methacrylic acid N then, the N-dimethylaminoethyl aqueous solution, it is suitable that the conditioned reaction temperature makes it inductive phase, after polymerization 2-20 hour, cooling, discharging, cutting, drying, pulverizing obtain polymer product.
The concrete preparation method of the methylpropene sodium sulfonate that the present invention adopts is as follows: commercially available S-WAT being purified, mix in the aqueous solution with methylallyl chloride, adjust to suitable pH value, is to react under 30～70 ℃ in temperature; After having reacted, the concentrating under reduced pressure reaction solution carries out heat filtering to finite concentration, removes the partial reaction by product, can obtain the raw product of methylpropene sodium sulfonate after the filtrate cooling, can obtain the methylpropene sodium sulfonate product after raw product being made with extra care again.The pH value of reaction intermediate value can be by adding SO
2Gas, sulfuric acid, hydrochloric acid, formic acid, acetate, sodium hydroxide, KOH, NH
3Or sulphite is regulated.
Ter-polymers oil-displacing agent of the present invention is applied in the oil recovery process.Concrete, be ter-polymers oil-displacing agent of the present invention to be mixed with certain density solution be applied in the oil recovery process.This solution has and keeps enough viscosity under working concentration and high temperature, high salinity condition, is suitable as the used for tertiary oil recovery polymer oil-displacing agent.
The present invention utilizes copolyreaction to introduce in the polymkeric substance containing sulfonic group vinyl functional monomer, improves the heat and salinity tolerance performance of polymkeric substance; Adopt hydrolysis reaction to make the oil-displacing agent polymkeric substance produce carboxyl, make the carboxyl and the sulfonic group that coexist in the polymkeric substance form spirane structure, hinder the salt positive ion and enter the aquation territory of carboxyl, thereby the oil-displacing agent salt resistance is improved greatly; Make the associating supramolecule cross-linked network of formation between polymkeric substance by crosslinking reaction, in high level salt solution, the small molecules ionogen strengthens the polymer hydrophobic association, shows tangible anti-salt property.
The temperature resistant antisalt performance of polymer oil-displacing agent of the present invention is represented with its anti-salt temperature-resistant viscosity retention ratio.Bu Luoke Field viscosity with NDJ-1 type rotary viscosity design determining polymers soln is calculated as follows viscosity retention ratio, is the anti-salt temperature-resistant viscosity retention ratio of polymer oil-displacing agent:
High temperature is preserved back viscosity in the anti-salt temperature-resistant viscosity retention ratio %=[simulation mining site water]/[25 ℃ of viscosity in the deionized water]
The premium properties of ter-polymers oil-displacing agent of the present invention shows:
1, this ter-polymers still can keep higher viscosity in high temperature and haline water solution, has good temperature resistant antisalt performance, this oil-displacing agent of measuring according to oilfield applications standard SY/T 5862-93 is 26 in total mineralization, the simulation mineral reserve water compound concentration of 000ppm is the polymers soln (oil field simulation mining site water) of 1000ppm, under 90 ℃, solution temperature resistant antisalt viscosity retention ratio after the preservation is 14.28-24.17%, is 1.67-2.76% apparently higher than plain polypropylene acid amides homopolymer oil-displacing agent temperature resistant antisalt viscosity retention ratio under the same conditions.
2, adopt K
2S
2O
8-NaHSO
4-DMAEMA except having good efficiency of initiation, also has the effect of linking agent as initiator, can make polymkeric substance produce little crosslinking structure, and further improves the viscosity of solution.
3, in a cover reaction unit, polystep reactions such as polymerization, crosslinked, hydrolysis are carried out simultaneously, simplify technological process, reduce production costs.
Embodiment
Use the Bu Luoke Field viscosity of this polymer flooding agent solution of NDJ-1 type rotary viscosity design determining in the embodiments of the invention.
The preparation of embodiment 1 methylpropene sodium sulfonate
Take by weighing S-WAT 120g, be dissolved in the 480ml deionized water, it is 10.5 that the Ph value is adjusted with sodium hydroxide or dilute hydrochloric acid in the dissolving back, place 26 hours after-filtration, filtrate adding agitator is housed to, thermometer, in the four-hole reaction flask of reflux exchanger, adjusting the pH value with sodium hydroxide or dilute hydrochloric acid is 9.6, takes by weighing methylallyl chloride 93g and adds in the reaction flask, be warming up to 66.5 ℃, reacted 3 hours, and under reduced pressure reaction solution was concentrated then, slough liquid 186ml, carry out heat filtering, remove byproduct of reaction, after the filtrate cooling, the saturated solution 600ml with methylpropene sodium sulfonate mixes stirring again, crystallization then, filter, drying obtains the methylpropene sodium sulfonate product.
Embodiment 2
With acrylamide 71g, the methylpropene sodium sulfonate 0.71g that embodiment 1 obtains, N,N-DMAA 2.07g are dissolved in the 143g deionized water, add to be equipped with in the four neck polymerization bottles of thermometer, agitator, nitrogen conduit and reflux exchanger.
With NaOH or dilute hydrochloric acid regulator solution pH value to 7～9, add b diammonium edta sodium 0.175g again and stir, adjust 45 ℃ of starting temperatures, fed nitrogen 30 minutes, add the aqueous solution 5g that contains 4% Potassium Persulphate and 0.6% S-WAT.After 10 minutes, add 0.02g DMAEMA, polymerization hydrolysis reaction 4 hours, discharging, cutting is pulverized after 50 ℃ of vacuum-dryings, obtains white powdery solid.The product hydrolysis degree is 15%, and the weight content of sulfonic acid group is 0.85%.With the deionized water compound concentration is the polymers soln of 1000ppm, measures its Bu Luoke Field viscosity in the time of 25 ℃, and data are listed table 1 in.
Embodiment 3
With acrylamide 71g, methylpropene sodium sulfonate 0.71g, N,N-DMAA 2.07g are dissolved in the 143g deionized water, add to be equipped with in the four neck polymerization bottles of thermometer, agitator, nitrogen conduit and reflux exchanger.
With NaOH or dilute hydrochloric acid regulator solution pH value to 6～7, add b diammonium edta sodium 0.175g again and stir, adjust 35 ℃ of starting temperatures, fed nitrogen 30 minutes, add the aqueous solution 5g that contains 4% Potassium Persulphate and 0.6% S-WAT.After 10 minutes, add 0.02g DMAEMA, polymerization hydrolysis reaction 4 hours, discharging, cutting is pulverized after 50 ℃ of vacuum-dryings, obtains white powdery solid.The product hydrolysis degree is 5%, and the weight content of sulfonic acid group is 0.88%.With the deionized water compound concentration is the polymers soln of 1000ppm, measures its Bu Luoke Field viscosity in the time of 25 ℃, and data are listed table 1 in.
Embodiment 4
With acrylamide 51.65g, methylpropene sodium sulfonate 14.76g, N,N-DMAA 7.37g are dissolved in the 143g deionized water, adding is equipped with in the four neck polymerization bottles of thermometer, agitator, nitrogen conduit and reflux exchanger, and other operation is identical with embodiment 1.
Reaction finishes and obtains white powdery solid, and the product hydrolysis degree is 15%, and the weight content of sulfonic acid group is 18.6%.With the deionized water compound concentration is the polymers soln of 1000ppm, measures the Bu Luoke Field viscosity of 25 ℃ of this solution, and data are listed table 1 in.
Comparative example 1
With acrylamide 75g, be dissolved in the 143g deionized water, adding is equipped with in the four neck polymerization bottles of thermometer, agitator, nitrogen conduit and reflux exchanger.
With NaOH or dilute hydrochloric acid regulator solution pH value to 8～9, add b diammonium edta sodium 0.175g again and stir, adjust 45 ℃ of starting temperatures, fed nitrogen 30 minutes, add 4% Potassium Persulphate, 0.6% sodium sulfite aqueous solution 5g.Polymerization hydrolysis reaction 4 hours, discharging, cutting is pulverized after 50 ℃ of vacuum-dryings, obtains white powdery solid.The product hydrolysis degree is 15%.With the deionized water compound concentration is the polymers soln of 1000ppm, measures the Bu Luoke Field viscosity of 25 ℃ of this solution, and data are listed table 1 in.
Comparative example 2
With acrylamide 75g, be dissolved in the 143g deionized water, adding is equipped with in the four neck polymerization bottles of thermometer, agitator, nitrogen conduit and reflux exchanger.
With NaOH or dilute hydrochloric acid regulator solution pH value to 10.5～11.5, add b diammonium edta sodium 0.175g again and stir, adjust 55 ℃ of starting temperatures, fed nitrogen 30 minutes, add 4% Potassium Persulphate, 0.6% sodium sulfite aqueous solution 5g.Polymerization hydrolysis reaction 4 hours, discharging, cutting is pulverized after 50 ℃ of vacuum-dryings, obtains white powdery solid.The product hydrolysis degree is 25%.With the deionized water compound concentration is the polymers soln of 1000ppm, measures the Bu Luoke Field viscosity of 25 ℃ of this solution, and data are listed table 1 in.
Embodiment 5
To embodiment 2-4, the polymkeric substance that comparative example 1,2 is produced carries out the salt tolerant heat stability test.Concrete grammar is that (industry standard SY/T 5862-93) is 26 with total mineralization, and the simulation mineral reserve water compound concentration of 000ppm is the polymers soln of 1000ppm, with pack in test tube polymers soln more than the 30ml of the method for finding time.With the thermal-flame tube sealing and be placed in 90 ℃ of thermostat containers and preserved 90 days.Measure the Bu Luoke Field viscosity of the polymers soln of 1000ppm in the Bu Luoke Field viscosity of this solution and the 25 ℃ of following deionized waters respectively, and calculate its anti-salt temperature-resistant viscosity retention ratio, data are listed table 1 in.
The anti-salt temperature-resistant test-results of table 1 polymkeric substance
| Viscosity (mPa.s) | |||
| Deionized water (25 ℃) | Simulation mining site water (90 ℃) | Viscosity retention ratio (%) | |
| Embodiment 2 embodiment 3 embodiment 4 comparative examples 1 comparative example 2 | 266 120 138 326 418 | 38 29 21 9 7 | 14.28 24.17 15.22 2.76 1.67 |
Can find out from table 1, ter-polymers of the present invention in total mineralization be 26000ppm simulation mining site water in 90 ℃ preserve 90 days after, viscosity is that 21-38mPa.s, anti-salt temperature-resistant viscosity retention ratio are 14.28-24.17%; Under the similarity condition, the viscosity of methacrylamide homopolymer is 7-9mPa.s, and the anti-salt temperature-resistant viscosity retention ratio is 1.67-2.76%; Ter-polymers performance of the present invention is apparently higher than methacrylamide homopolymer, so have significant anti-salt temperature-resistant ability.
Claims (8)
1, a kind of ter-polymers oil-displacing agent comprises the polymkeric substance that is obtained through polyreaction by following component: by the adding total monomer weight,
A) acrylamide of 60%-99.96% (weight);
B) methylpropene sodium sulfonate of 0.006%-25% (weight);
C) N,N-DMAA of 0.01%-15% (weight);
The content of sulfonic acid group is 0.5-22.7% (weight) in this polymkeric substance, and described (b) component methylpropene sodium sulfonate is obtained by methylallyl chloride and S-WAT reaction, and the pH value of reaction is controlled at 8.5-10.0.
2, according to the described ter-polymers oil-displacing agent of claim 1, the ph value of reaction that it is characterized in that described preparation methylpropene sodium sulfonate is 9.0-9.8.
3, according to the described ter-polymers oil-displacing agent of claim 1, it is characterized in that described polyreaction, add polynary initiator polymerization by adding total monomer weight, used initiator is persulphate 0.0005%-0.007% (weight); Sodium bisulfite 0.00003%-0.0005% (weight); Methacrylic acid N, N-dimethylaminoethyl 0.0002%-0.006% (weight).
4, according to the described ter-polymers oil-displacing agent of claim 1, it is characterized in that described polymkeric substance obtains through solution polymerization, monomeric gross weight is the 10-45% of weight of solvent.
5,, it is characterized in that described polymerization reaction time is 2-20 hour according to the described ter-polymers oil-displacing agent of claim 1.
6, according to the described ter-polymers oil-displacing agent of claim 1, it is characterized in that:
Described polymkeric substance obtains through solution polymerization, and monomeric gross weight is the 10-45% of weight of solvent;
Add polynary initiator by adding total monomer weight, used initiator is persulphate 0.0005%-0.007% (weight); Sodium bisulfite 0.00003%-0.0005% (weight); Methacrylic acid N, N-dimethylaminoethyl 0.0002%-0.006% (weight);
Described polymerization reaction time is 2-20 hour.
7, the preparation method of the described ter-polymers oil-displacing agent of one of claim 1～6, this method may further comprise the steps:
(1) preparation methylpropene sodium sulfonate
Being mixed in the aqueous solution by methylallyl chloride and S-WAT, is 30～70 ℃ of reactions down in temperature, and pH value is controlled at 8.5-10.0;
(2) preparation of ter-polymers
The acrylamide, the N that in polymeric kettle, add required weight, N-DMAA and homemade methylpropene sodium sulfonate, making total monomer weight with the deionized water adjusting is the 10-45% of weight of solvent, the pH value of conditioned reaction liquid is 5-11.5, feed nitrogen down at starting temperature 15-70 ℃, the aqueous solution that adds Potassium Persulphate and S-WAT, add methacrylic acid N then, the N-dimethylaminoethyl aqueous solution, it is suitable that the conditioned reaction temperature makes it inductive phase, after polymerization 2-20 hour, cooling, discharging, cutting, drying, pulverizing obtain polymer product.
8, the application of the described ter-polymers oil-displacing agent of one of claim 1～6 in oil recovery process.
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| CN100378190C (en) * | 2005-07-26 | 2008-04-02 | 中国科学院理化技术研究所 | Nano water-soluble microgel oil displacement material and preparation method thereof |
| CN100558845C (en) * | 2005-09-30 | 2009-11-11 | 中国科学院理化技术研究所 | Core-shell self-crosslinking acrylamide copolymer deep profile control water shutoff agent and preparation method thereof |
| CN1298804C (en) * | 2005-10-18 | 2007-02-07 | 中国石油天然气股份有限公司 | Hydrophobic water-swelling profile control agent |
| CN101775275B (en) * | 2010-01-18 | 2013-03-20 | 中国石油化工股份有限公司胜利油田分公司 | Novel viscoelastic particle oil displacement agent and preparation method thereof |
| CN102373049B (en) * | 2010-08-23 | 2013-07-31 | 中国石油化工股份有限公司 | Oil displacement method used for improving recovery efficiency of tertiary oil recovery |
| CN102464783B (en) * | 2010-11-05 | 2013-03-27 | 中国石油化工股份有限公司 | Water-soluble thermo-thickening copolymer, and preparation method and application thereof |
| CN102464781B (en) * | 2010-11-05 | 2013-02-27 | 中国石油化工股份有限公司 | Thermothickening terpolymer, its preparation method and application |
| CN102464782B (en) * | 2010-11-05 | 2013-02-27 | 中国石油化工股份有限公司 | Thermo-thickening water-soluble tricopolymer, its preparation method and application |
| CN102464761B (en) * | 2010-11-17 | 2013-09-18 | 中国石油化工股份有限公司 | Sulphonated heat resistant and salt tolerant copolymer for oil field and preparation method thereof |
| CN103665260B (en) * | 2012-09-05 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of temperature resistant antisalt Polymer Used For Oil Displacement and preparation method thereof |
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