CN104448127A - Polymer mobility control agent suitable for ultrahigh-salinity oil deposit and preparation method thereof - Google Patents
Polymer mobility control agent suitable for ultrahigh-salinity oil deposit and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a polymer mobility control agent suitable for an ultrahigh-salinity oil deposit and a preparation method thereof, and the polymer mobility control agent is mainly used for solving the problem that a polymer can not meet the requirement for tertiary oil recovery due to poor temperature resistant property, salt resistant property and shearing resistant property in the prior art. In order to better solve the problem, the technical scheme adopted by the invention is as follows: the control agent for an amphoteric hydrophobic associated polymer comprises the following components in parts by weight of the amphoteric hydrophobic associated polymer: 5-99.9 parts of nonionic water-soluble monomers, 0-50 parts of anionic monomers or/and cationic monomers, 0.1-10 parts of hydrophobic monomers with surface activity, 0.1-5 parts of inorganic substances and 1-20 parts of surface active agents. The preparation method disclosed by the invention can be used for the industrial production of the polymer mobility control agent suitable for the ultrahigh-salinity oil deposit.
Description
Technical field
The present invention relates to a kind of polymkeric substance mobility control agent being applicable to special high salinity reservoirs and preparation method thereof.
Background technology
Domestic each elephant through once, secondary oil recovery, crude oil water content constantly increases, and part elephant successively enters tertiary phase.Polymer flooding is the main technique methods of tertiary oil recovery, and oil-displacement mechanism is clear, and technique is relatively simple, and technology reaches its maturity, and is one and effectively improves recovery efficiency technique measure.The oil-displacement mechanism of polymkeric substance mainly utilizes the viscosity of water-soluble polyacrylamide molecular chain, improves the mobility ratio of displacing fluid, improves efficiency of displacement and swept volume, thus reaches the object improving recovery ratio.Because the tertiary oil recovery cycle is long, deep layer oil temperature is high, and therefore, polymkeric substance used for tertiary oil recovery must have good thickening, heatproof, anti-salt, shear resistant, and performance is steady in a long-term.
The Industrial products being usually used in the polymer flooding of enhanced oil recovery (EOR) in early days only have partially hydrolyzed polyacrylamide (PAM), and it depends on the repulsive interaction of ion on high molecular and polymer molecular chain and strong polarity side base and reaches Efficient Adhesive Promotion.But high-molecular weight polymer, when being subject to larger stretching and shear-stress, is easy to mechano-degradation and loses viscosity occur, particularly evident during injection of polymer in low permeability rock stratum.Positively charged ion in the aqueous solution, especially divalent ion, the ionic group in meeting shielded polymer, makes polymer molecular chain curling, and hydrodynamic volume reduces even to precipitate, thus tackifying is reduced greatly.When depth of stratum reaches 20000 feet, reservoir temperature higher (about 100 DEG C), the facile hydrolysis in high-temperature water solution of the amide group in polyacrylamide (PAM), makes the salt resistance of polymers soln sharply decline.In recent years, about the research of temperature-resistant and anti-salt type polyacrylamide mainly through introducing the thermostability of large side base or rigidity side base raising polymkeric substance, the monomer of introducing suppression hydrolysis or carrying out copolymerization to improve hydrolysis and the anti-salt property of polymkeric substance to the insensitive monomer of salt on main polymer chain, or improve the temperature resistant antisalt performance of polymkeric substance by the heat resistance and salt tolerance of hydrophobic grouping.But make polymkeric substance be difficult to reach high molecular due to the quality of comonomer or price or product has higher cost, in industrial production or some restrictions can be subject in tertiary oil recovery practical application.In current tertiary oil recovery, the polymkeric substance that can meet temperature resistant antisalt requirement is little, be not price too higher position be unstable properties, particularly can not meet more than salinity 100000mg/L, the requirement of more than 85 DEG C high temperature.
Hydrophobic associated water-soluble polymer refers to the class water-soluble polymers with a small amount of hydrophobic grouping on polymer hydrophilicity macromolecular chain.Due to the thickening of its uniqueness, anti-salt, the SOLUTION PROPERTIES such as anti-shearing, be applied to high salt as novel polymeric oil-displacing agent, high-shear oil reservoir development has a good application prospect.The hydrophobic association type multipolymer generated because of introducing hydrophobic grouping in polymer molecule, in water medium, its hydrophobic chain link is assembled to be similar to tensio-active agent mode and to associate, effective hydrodynamic volume of a macromole ball of string increases, water medium viscosity improves, larger side base plays shielding effect to polymer molecule backbone, weakens the p-COO of salt ion
-the impact of group; And larger side base also has certain space steric effect, strengthen chain rigidity.
But now there are some researches show this base polymer associative ability and water-soluble between conflicting, the carbochain of the polymkeric substance of good water solubility often hydrophobic monomer is shorter or content is lower, associating effect is not obvious, just need show certain association effect and meet heat and salinity tolerance performance under higher polymer concentration; And the polymer associate containing the hydrophobic monomer of long-chain or high-content is very capable, heat and salinity tolerance performance is good, but poorly water-soluble, often need long time to dissolve completely, lose the value of industrial applications.How can find desirable trim point between, be the key that can this base polymer be widely used in tertiary oil recovery process.
Domesticly in hydrophobic associated polymer, carried out large quantity research, wherein Southwest Petroleum Institute, Chengdu Univ. of Science & Technology, exploratory development research institute of PetroChina Company Limited., University of Petroleum, Northcentral University etc. all achieve progress and achievement preferably.
Feng Rusen etc. (CN1793189A) have adopted micella copolymerization method to synthesize containing the hydrophobic associated polymer of acrylamide, sodium acrylate and allyl group-alkyl phenyl ether three kinds of structural units, although there is good Efficient Adhesive Promotion, the synthesis of allyl group-alkyl phenyl ether monomer is comparatively complicated; Zhong Chuanrong etc. (CN101293944A, CN 101148582A) have synthesized containing the hydrophobic associated polymer of vinyl condensed-nuclei aromatics as hydrophobic monomer, the polymerization process time is longer, only have rated the Efficient Adhesive Promotion of polymkeric substance in fresh water and salt solution at 45 DEG C, anti-salt effect assessment NaCl concentration <100000mg/L, CaC1
2the situation of concentration <1000mg/L; Ou Yangjian etc. (CN1317501) high-molecular hydrophobic associated polymkeric substance, at 75 DEG C of total mineralization 12000mg/L, wherein Ca
2+and Mg
2+for 300mg/L, sample concentration is 1500mg/L, and adopt Brookfield viscometer, shearing rate is 36.7s
-1viscosity is 15.6 ~ 12.4mPa.s; Kong Ying etc. (CN1528734, CN1528797) have synthesized the water-soluble hydrophobic associated type polymkeric substance of ultra-high molecular weight containing fluorocarbon group, have rated it at triumph salt solution (total mineralization 6000mg/L, calcium ions and magnesium ions 500mg/L) tackifying under 70 DEG C of conditions, wherein fluorinated acrylate hydrophobic monomer is expensive; Jiang Liding (synthesis of new gang hydrophobic association polyacrylamide and the rheological property of the aqueous solution thereof, Master's thesis in 2007) adopts surface active monomer NaAMC
14the method of S and AM aqueous solution homogeneous phase copolymerization has successfully prepared the multipolymer NaAMC with hydrophobic block structure
14s/AM, overcomes some shortcomings that micellar co-polymerization uses conventional surfactants to bring, multipolymer NaAMC
14the length of hydrophobic micro-block of S/AM can control by regulating additional electrolytical consumption, but research work biases toward theory, the evaluation result not under the mineral reserve condition of actual oil field.
Make a general survey of above-mentioned research, the most frequently used method of current synthetizing hydrophobic associated polymkeric substance is micellar free radical copolymerization method, needing to add a large amount of tensio-active agents (as SDS) when adopting this kind of method to be polymerized makes hydrophobic monomer solubilising in micella, but add the association behavior of a large amount of tensio-active agents on polymkeric substance in the course of the polymerization process and have significant impact, these tensio-active agents interact with hydrophobic segment in polymerisate, deteriorate the performance of hydrophobic associated water-soluble polymer.If remove these tensio-active agents, the complicacy of the last handling processes such as separation and purifying can be increased.In order to simplify last handling process and strengthen structure adaptability, can adopt and inherently there is surface-active hydrophobic monomer.This kind of monomer containing hydrophobic grouping and hydrophilic radical, does not need when copolymerization to add tensio-active agent in addition, can directly adopt traditional free yl solution polymerization simultaneously, and can make in hydrophobic monomer height unordered irregularly introducing multipolymer.But there is research (Ezzell abroad, S.A., McCormick, C.L., Macromolecules 1992,25 (7), 1881 ~ 1886) find, the multipolymer critical association concentration in aqueous of this kind of ionic hydrophobic monomer is more than 2 times of the identical Hydrophobic chain length of micella multipolymer, and this is totally unfavorable to hydrophobic associated polymer application industrially.As can be seen here, domestic and international researchist is to structure, character, the viscosifying mechanisms of hydrophobic associated water-soluble polymer and should be used as large quantity research, exploration work, but the evaluation of polymkeric substance is substantially according to grand celebration or some mineral reserve condition of Shengli Oil Field, temperature and salinity do not belong to high temperature and high salt type, for more than salinity 100000mg/L, the condition of more than 85 DEG C high temperature does not almost relate to.
The present invention is to ionic, the synthesis of both sexes hydrophobic associated water-soluble polymer and hydrophobically modified polyelectrolyte, structural characterization and SOLUTION PROPERTIES aspect are carried out extensively, on deep Research foundation, utilize the interaction had between surface-active monomer and the ionic comonomer of its opposite charges, one is that ionic comonomer effects on surface reactive monomer has solublization, separately tensio-active agent need not be added when being polymerized, two is to form both sexes hydrophobic associated polymer, even if polymkeric substance also has high-effective viscosity and excellent heatproof under hydrophobic monomer lower aq, anti-salt and shear resistant, in rear hydrolytic process except adding conventional alkali, also add a certain amount of tensio-active agent, contribute to structure adaptability and play collaborative viscosifying action.The polymkeric substance mobility control agent being applicable to special high salinity reservoirs of the present invention has high tackifying, normal salt sensitivity (meet salt retrogradation), the positive Thermo-sensitive (intensification retrogradation) of certain limit and lower micelle-forming concentration, and excellent anti-aging, anti-shear ability, be suitable for the requirement of total mineralization more than 100,000 oil reservoir oil displacements, have a good application prospect in tertiary oil recovery engineering.
Summary of the invention
One of technical problem to be solved by this invention is the problem that the high temperature resistant anti-high salinity of polymkeric substance that exists in prior art and shear resistant can meet tertiary oil recovery and require, there is provided a kind of polymkeric substance mobility control agent being applicable to special high salinity reservoirs, this polymkeric substance has high-effective viscosity, temperature resistant antisalt (the chance salt retrogradation of certain limit, intensification retrogradation), the feature that thermally-stabilised and anti-shear performance is excellent.
Two of technical problem to be solved by this invention is to provide the preparation method of the polymkeric substance in one of a kind of technical solution problem, and it is simple that the method has polymerisation process, without the need to steps such as separation, purifying, and the advantage reduced costs.
In order to one of solve the problems of the technologies described above, the present invention is as follows by the following technical solutions: a kind of polymkeric substance mobility control agent being applicable to special high salinity reservoirs, the molecular weight of this polymkeric substance is between 200-2000 ten thousand, and the solution be made up of following monomer reacts obtained under the existence of composite initiator; The solution of described monomer composition, with weight parts, comprises following component:
A) nonionic water-soluble monomers of 5 ~ 99.9 parts;
B) 0 ~ 50 part of anionic monomer is or/and cationic monomer;
C) 0.1 ~ 10 part there is surface-active hydrophobic monomer;
D) 0.1 ~ 5 part of inorganics;
E) 1 ~ 20 part of tensio-active agent
F) water of 200 ~ 2000 parts;
Wherein, described composite initiator, in above-mentioned whole weight percent monomer, comprises following component:
The persulphate of (a) 0.003 ~ 0.5%;
The sulphite of (b) 0.003 ~ 0.5% or bisul-phite;
(c) 0.003 ~ 1% by NR
1r
2r
3representative tertiary amine compounds or by N
+r
4r
5r
6r
7representative quaternary ammonium compounds or by NH
2r
8the fat amine compound of representative, R in formula
1~ R
7all be selected from C
1~ C
14straight or branched alkyl or alkyl derivative, R
8be selected from C
1~ C
18straight or branched alkyl or alkyl derivative;
The azo compound of (d) 0.005 ~ 1%;
The urea of (e) 0.01 ~ 10%, thiocarbamide;
The disodium ethylene diamine tetraacetate of (f) 0.03 ~ 0.5% or diethylene triamine pentacetic acid (DTPA) sodium;
The molecular weight regulator of (g) 0.03 ~ 0.5%.
In technique scheme, described nonionic water-soluble monomers preferred version is for being selected from water-soluble vinyl monomer, and described vinyl monomer is selected from least one in acrylamide, Methacrylamide, NIPA, N-N-DMAA, N-N-acrylamide and N hydroxymethyl acrylamide, N-vinyl formamide, N-vinyl acetamide, N-vinyl pyridine and NVP.Described anionic monomer preferred version is be selected from least one in 2-acrylamide-2-methylpro panesulfonic acid, vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid, fumaric acid, β-crotonic acid, vinylbenzenesulfonic acid, vinyl sulfonic acid, vinyl phosphonate, allyl sulphonic acid, allyl phosphonic acid and/or its water-soluble alkali, alkaline-earth metal and ammonium salt; Cationic monomer is selected from least one in dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and 2-acrylamido-2-trimethoxysilyl propyl methacrylate ammonium chloride.
It is described that to have surface-active hydrophobic monomer preferred version be anionic surface activity monomer or cationic surfactant monomer.Described have surface-active hydrophobic monomer more preferably scheme be the mono-vinyl compounds being selected from 8-22 carbon atom.Preferred technical scheme, described anionic surface activity monomer to be vinyl carbochain number be 8 ~ 18 acrylamide azanyl sodium sulfonate; Cationic surfactant monomer to be vinyl carbochain number be 12 ~ 22 allyl alkyl ammonium chloride.
Described inorganics preferred version be acidic oxide as boron oxide, silicon oxide etc., basic oxide are as barium oxide, manganese oxide, calcium oxide, magnesium oxide etc. and intermediate oxide aluminum oxide, zinc oxide etc.They or generation great amount of hydroxy group soluble in water or can react with anionic monomer and generate salt, make the amphiphilic polymers with hydrophobic associative behavior define variable network structure by the effect of hydrogen bond or other chemical bonds, under high salinity, high temperature or shearing action, there is better viscosity stability.
Persulphate preferred version is for being selected from Potassium Persulphate, Sodium Persulfate or ammonium persulphate; Sulphite is selected from S-WAT or potassium sulfite, and bisul-phite is selected from sodium bisulfite or Potassium hydrogen sulfite; Tertiary amine compounds preferred version for being selected from methacrylic acid N, N-dimethylaminoethyl, vinylformic acid N, N-dimethylaminoethyl, β-dimethylaminopropionitrile, Tetramethyl Ethylene Diamine, vulkacit H etc.; Quaternary ammonium compounds is selected from N, N-dimethyl diallyl ammonium chloride, N, N-diethyl diallyl ammonium chloride; Fat amine compound is selected from methylamine, quadrol, 1,3-propylene diamine, Putriscine, N, N-dimethyl-1,3-propylene diamine etc.; Azo compound is selected from azo diisobutyl amidine hydrochloride, 2,2'-azos [2-(2-tetrahydroglyoxaline-2-base) propane] dihydrochloride etc.; Molecular weight regulator preferred version is be selected from least one in Virahol, the trimethyl carbinol, isopropylcarbinol, tetramethylolmethane or dipropylene glycol.
In order to solve the problems of the technologies described above two, the present invention is as follows by the following technical solutions: a kind of preparation method being applicable to the polymkeric substance mobility control agent of special high salinity reservoirs, comprises following step successively:
A () adds water, nonionic water-soluble monomers, anionic monomer in a kettle. or/and cationic monomer, have the auxiliary agents such as surface-active hydrophobic monomer and inorganics;
B () adds the composite initiation system of part, stir, and forms solution;
PH value to 7 ~ 10 of (c) regulator solution, and pass into nitrogen, temperature in the kettle is down to 10 ~ 30 DEG C, then adds remaining composite initiator, after continuing to pass into nitrogen, sealing;
D temperature of reaction was risen to 40 ~ 60 DEG C after 0.5 ~ 1 hour by () gradually, react after 2 ~ 8 hours, obtain gel polymerisate;
E () added the composite hydrolysis agent containing tensio-active agent after cutting glue, 80 ~ 90 oC hydrolysis reaction 2 ~ 4 hours; Then vacuum-drying 3 ~ 6 hours at 60 ~ 90 DEG C, is crushed to certain particle size with pulverizer or rolling machine, obtains the polymkeric substance mobility control agent being applicable to special high salinity reservoirs.
In technique scheme, preferred technical scheme, described composite hydrolysis agent, in the whole weight percent monomer of association polymer, comprises following component: at least one in the sodium hydroxide of (a) 0 ~ 10% or sodium carbonate; (b) 0.5 ~ 50% tensio-active agent.
Described tensio-active agent preferred version is for being selected from aniorfic surfactant as C
8-16sodium alkyl sulfate, C
8-16sodium alkyl benzene sulfonates etc., cationic surfactant is as C
8-16alkyl trimethyl bromine (chlorine) changes ammonium etc., and non-ionic type is as alkylphenol polyoxyethylene (EO=4 ~ 30) or their any mixture;
In technique scheme, polymkeric substance mobility control agent of special high salinity reservoirs and preparation method thereof, comprise the following steps: first add a certain amount of deionized water in a kettle., then drop into acrylamide, surface active monomer and negatively charged ion and/or cationic monomer and other auxiliary agents and be stirred to and dissolve completely.With NaOH solution adjust ph to 7 ~ 10, and start to pass into high pure nitrogen, after 10 ~ 60min, temperature in the kettle is down to specified temperature (10 ~ 30 DEG C), then adds composite initiator successively, seal after continuing logical nitrogen 10 ~ 60min.After 0.5 ~ 2 hour, temperature of reaction is risen to gradually specified temperature (40 ~ 60 DEG C), react and obtain gel polymerisate after 2 ~ 8 hours, the composite hydrolysis agent aqueous solution containing tensio-active agent and alkali is added after cutting glue, 80 ~ 90 oC hydrolysis reaction 2 ~ 4 hours, then vacuum-drying 3 ~ 6h at 60 ~ 90 DEG C, smashes the rear sampling analysis of screening with pulverizer or rolling machine.
The polymkeric substance mobility control agent being applicable to special high salinity reservoirs be by adopt 5 ~ 99.9 parts of nonionic water-soluble monomers, 0 ~ 50 part of negatively charged ion or/and cationic monomer, 0.1 ~ 10 part there is surface-active hydrophobic monomer, 0.1 ~ 5 part of inorganics, under composite initiation system exists, cause the aqueous solution polymerization of comonomer, then add composite hydrolysis agent as required and carry out rear hydrolysis reaction, final drying is pulverized, obtain solid content about 90%, degree of hydrolysis 5 ~ 30%, the polymkeric substance of molecular weight 200-2000 ten thousand, there is high-effective viscosity and normal salt sensitivity (meeting salt retrogradation) under high temperature and high salt condition, the positive Thermo-sensitive (intensification retrogradation) of certain limit and lower micelle-forming concentration, and there is better solvability, long-term thermal stability and anti-shear performance, the requirement of more than 100,000 salinity high-temperature oil reservoir Polymer Used For Oil Displacements is met in tertiary oil recovery.This technique is simple to operation, is applicable to scale operation.
Polymkeric substance mobility control agent being applicable to special high salinity reservoirs that the present invention relates to and preparation method thereof, owing to have employed the ion monomer contrary with having surface active monomer ion characteristic, both interaction effects on surface reactive monomers have solublization, separately need not add tensio-active agent when being polymerized; Even and if the both sexes hydrophobic association polymerization polymkeric substance under hydrophobic monomer lower aq obtained also has excellent temperature resistant antisalt, thermally-stabilised and anti-shear performance; The inorganics added makes the amphiphilic polymers with hydrophobic associative behavior define variable network structure by the effect of hydrogen bond or other chemical bonds in reaction system, under high salinity, high temperature or shearing action, have better viscosity stability; And have employed composite initiation system, and supporting with it with preferred technique, therefore reacting balance, be conducive to chainpropagation, molecular weight of product is controlled, the rear hydrolysis process adopted, owing to the addition of tensio-active agent, contributes to structure adaptability and plays collaborative viscosifying action.Polymkeric substance mobility control agent being applicable to special high salinity reservoirs using preparation technology provided by the present invention to obtain and preparation method thereof, molecular weight is adjustable between 200 ~ 2,000 ten thousand, excellent viscosifying action is shown under high temperature and high salinity, the sticky dense curve display of polymkeric substance, this both sexes hydrophobic associated polymer mixture has stronger association, viscosity amplification can reach two to three orders of magnitude, and micelle-forming concentration appears at below 2000mg/L; Polymkeric substance has salt thickening effect more than 100,000 under salinity, viscosity-temperature curve shows, polymkeric substance viscosity 60 ~ 80 DEG C time obviously increases, and to decline but still higher than the viscosity before 60 DEG C though have afterwards; Ageing-resistant and the anti-shear performance of polymkeric substance is good, can be used in the tertiary oil recovery of extra-high salinity high-temperature oil reservoir.
Below by specific embodiment, the present invention will be further elaborated.
Embodiment
[embodiment 1]
First add in 2500g deionized water in a kettle., add 430g acrylamide (AM), 2-acrylamido-2-methyl propane sulfonic acid (AMPS) 150g, 2.5g2-acrylamido tetradecyl sodium sulfonate (NaAMC
14s), 3.5g acrylyl oxy-ethyl-trimethyl salmiac (DAC), be neutralized to neutrality with NaOH, add disodium ethylene diamine tetraacetate 0.04g, urea 7g, Virahol 0.07g subsequently, be stirred to and dissolve completely.By NaOH adjust ph to 8.9, and start to pass into high pure nitrogen, after 30min, temperature in the kettle is down to 15 DEG C, then the aqueous solution of sodium bisulfite 10g of 0.2% is added successively, 0.5% methacrylic acid N, N-dimethylaminoethyl (DMAEMA) aqueous solution 10g, the azo diisobutyl amidine hydrochloride 10g of 0.5%, the persulfate aqueous solution 10g of 0.3%, seals after continuing logical nitrogen 30min.After 1 hour, temperature of reaction is risen to 48 DEG C gradually, react and obtain gel polymerisate after 3.5 hours, the composite hydrolysis agent 500g aqueous solution containing 35g sodium lauryl sulphate and 25gNaOH is added after cutting glue, 90 oC hydrolysis reaction 2 hours, then vacuum-drying 5h at 75 DEG C, smashes the rear sampling analysis of screening with pulverizer.
Testing solid content by GB/T12005.2-89 polyacrylamide determination of solid content method is 89.5%, Shi Jian≤90min is separated by GB/T12005.8-89 powdered polypropylene acid amides measuring of dissolution velocity method test Rong, testing degree of hydrolysis by GB/T12005.6-89 partially hydrolyzed polyacrylamide degree of hydrolysis measuring method is 11.6%, measure (viscosimetry) by GB/T12005.10-92 Molecular Weight for Polyacrylamide and measure intrinsic viscosity, and by [η]=3.73 × 10
-4mw
0.66calculating molecular weight is 9,120,000.Apparent viscosity is:
(1) at 95 DEG C, salt solution total mineralization 157726 mg/L, Ca
2++ Mg
2+: 1500mg/L polymer concentration solution under 6310 mg/L, adopts Brookfield viscometer, shearing rate 7.34s
-1under apparent viscosity be 107mPas.95 DEG C of viscosity retention ratios after aging 30 days are respectively 91%, and after high-speed shearing machine 5000rpm down cut 30min, viscosity retention ratio is 86%.
(2) at 95 DEG C, salt solution total mineralization 18000mg/L, Ca
2++ Mg
2+: 1500mg/L polymer concentration solution under 5700 mg/L, adopts Brookfield viscometer, shearing rate 7.34s
-1under apparent viscosity be 163mPas.95 DEG C of viscosity retention ratios after aging 30 days are respectively 92%, and after high-speed shearing machine 5000rpm down cut 30min, viscosity retention ratio is 89%.
[embodiment 2]
First add in 2600g deionized water in a kettle., add 480g acrylamide (AM), 2-acrylamido-2-methyl propane sulfonic acid (AMPS) 130g, 3.0g2-acrylamido sodium laurylsulfonate (NaAMC
12s) and 4.2g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC), be neutralized to neutrality with NaOH, add disodium ethylene diamine tetraacetate 0.045g, urea 7.0g, Virahol 0.06g, Alumina gel 15g subsequently, be stirred to and dissolve completely.By NaOH adjust ph to 9.0, and start to pass into high pure nitrogen, after 30min, temperature in the kettle is down to 16 DEG C, then the aqueous solution of sodium bisulfite 10.2g of 0.2% is added successively, 0.5% vinylformic acid N, N-dimethylaminoethyl (DA) aqueous solution 11g, the azo diisobutyl amidine hydrochloride 11.9g of 0.5%, the persulfate aqueous solution 11.2g of 0.3%, seals after continuing logical nitrogen 30min.After 1 hour, temperature of reaction is risen to 52 DEG C gradually, react and obtain gel polymerisate after 3 hours, the 500g aqueous solution containing 51g Sodium dodecylbenzene sulfonate and 32gNaOH is added after cutting glue, 90 oC hydrolysis reaction 2 hours, then vacuum-drying 5h at 75 DEG C, smashes the rear sampling analysis of screening with pulverizer.Evaluation result is in table 1.
[embodiment 3]
First add in 2700g deionized water in a kettle., add 500g acrylamide (AM), 2-acrylamido-2-methyl propane sulfonic acid (AMPS) 150g, vinylformic acid 130g, 3.2g2-acrylamido sodium cetanesulfonate (NaAMC
16s) and 5.2g dimethyl diallyl ammonium chloride (DMDAAC), be neutralized to neutrality with NaOH, add disodium ethylene diamine tetraacetate 0.05g, urea 8.0g, Virahol 0.07g, calcium oxide 0.5g subsequently, be stirred to and dissolve completely.By NaOH adjust ph to 9.5, and start to pass into high pure nitrogen, after 30min, temperature in the kettle is down to 20 DEG C, then the aqueous solution of sodium bisulfite 10.2g of 0.2% is added successively, 0.5% vinylformic acid N, N-dimethylaminoethyl (DA) aqueous solution 12.1g, 0.5% 2,2'-azo [2-(2-tetrahydroglyoxaline-2-base) propane] dihydrochloride 12g, the persulfate aqueous solution 11g of 0.3%, seal after continuing logical nitrogen 30min.After 1 hour, temperature of reaction is risen to 55 DEG C gradually, react and obtain gel polymerisate after 2.5 hours, after cutting glue, add the 400g aqueous solution containing 38gOP-20,90 oC hydrolysis reaction 2 hours, then vacuum-drying 5h at 75 DEG C, smashes the rear sampling analysis of screening with pulverizer.Evaluation result is in table 1.
[embodiment 4]
First add in 2600g deionized water in a kettle., add 510g acrylamide (AM), 2-acrylamido-2-methyl propane sulfonic acid (AMPS) 170g, 5.0g hexadecyldimethyl benzyl ammonium allyl ammonium chloride (C
16dMAAC) and 7.8g methacrylic acid (MAA), be neutralized to neutrality with NaOH, add disodium ethylene diamine tetraacetate 0.048g, urea 7.5g subsequently, trimethyl carbinol 0.08g, silicon sol 12g, be stirred to and dissolve completely.By NaOH adjust ph to 8.7, and start to pass into high pure nitrogen, after 30min, temperature in the kettle is down to 12 DEG C, then the aqueous solution of sodium bisulfite 11.2g of 0.2% is added successively, 0.5% methacrylic acid N, N-dimethylaminoethyl (DMAEMA) aqueous solution 12.6g, the azo diisobutyl amidine hydrochloride 12g of 0.5%, the persulfate aqueous solution 10.9g of 0.3%, seals after continuing logical nitrogen 30min.After 1 hour, temperature of reaction is risen to 52 DEG C gradually, react and obtain gel polymerisate after 3 hours, after cutting glue, add the 500g aqueous solution containing 42gOP-10 and 30gNaOH, 85oC hydrolysis reaction 2.5 hours, then vacuum-drying 4h at 80 DEG C, smashes the rear sampling analysis of screening with pulverizer.Evaluation result is in table 1.
[comparative example 1]
By 650g acrylamide monomer, disodium ethylene diamine tetraacetate 0.04g, urea 7g, Virahol 0.07g, adds in 2500g deionized water, stirs and dissolves completely, by NaOH solution adjust ph to 8.5.Then logical nitrogen 30min, and bath temperature is adjusted to 15 DEG C, then the aqueous solution of sodium bisulfite 10g of 0.2% is added successively, 0.5% methacrylic acid N, N-dimethylaminoethyl (DMAEMA) aqueous solution 10g, the azo diisobutyl amidine hydrochloride 10g of 0.5%, the persulfate aqueous solution 10g of 0.3%, seal after continuing logical nitrogen 30min.After 1 hour, temperature of reaction is risen to 50 DEG C gradually, react and obtain gel polymerisate after 3 hours, after cutting glue, add the hydrolytic reagent 730g aqueous solution containing 37gNaOH, 90 oC hydrolysis reaction 2 hours, then vacuum-drying 5h at 75 DEG C, smashes the rear sampling analysis of screening with pulverizer.
Testing solid content by GBT12005.2-89 polyacrylamide determination of solid content method is 88.92%, testing degree of hydrolysis by GBT12005.6-89 partially hydrolyzed polyacrylamide degree of hydrolysis measuring method is 11.3%, measure (viscosimetry) by GBT12005.10-92 Molecular Weight for Polyacrylamide and measure intrinsic viscosity, and by [η]=3.73 × 10
-4mw
0.66calculating molecular weight is 1,963 ten thousand.Apparent viscosity is in table 1.
[comparative example 2]
By 450g acrylamide (AM), 200g2-acrylamido-2-methyl propane sulfonic acid (AMPS), disodium ethylene diamine tetraacetate 0.04g, urea 7g, Virahol 0.07g, add in 2500g deionized water, stir and dissolve completely, by NaOH adjust ph to 9.0.Then logical nitrogen 30min, and bath temperature is adjusted to 15 DEG C, then the aqueous solution of sodium bisulfite 10g of 0.2% is added successively, 0.5% methacrylic acid N, N-dimethylaminoethyl (DMAEMA) aqueous solution 10g, the azo diisobutyl amidine hydrochloride 10g of 0.5%, the persulfate aqueous solution 10g of 0.3%, seal after continuing logical nitrogen 30min.After 1 hour, temperature of reaction is risen to 50 DEG C gradually, react and obtain gel polymerisate after 3 hours, after cutting glue, add the hydrolytic reagent 500g aqueous solution containing 25gNaOH, 90 oC hydrolysis reaction 2 hours, then vacuum-drying 5h at 75 DEG C, smashes the rear sampling analysis of screening with pulverizer.
Testing solid content by GBT12005.2-89 polyacrylamide determination of solid content method is 87.34%, testing degree of hydrolysis by GBT12005.6-89 partially hydrolyzed polyacrylamide degree of hydrolysis measuring method is 12.6%, measure (viscosimetry) by GBT12005.10-92 Molecular Weight for Polyacrylamide and measure intrinsic viscosity, and by [η]=3.73 × 10
-4mw
0.66calculating molecular weight is 1,365 ten thousand.Apparent viscosity is in table 1.
Table 1
* measure (viscosimetry) by GBT12005.10-92 Molecular Weight for Polyacrylamide and measure intrinsic viscosity, and by [η]=3.73 × 10
-4mw
0.66calculate molecular weight
* 1500mg/L polymer concentration solution is at 95 DEG C, 7.34s
-1under apparent viscosity,
Salt solution 1:TDS157726mg/L Ca
2++ Mg
2+6310mg/L,
Salt solution 2:TDS180000mg/L Ca
2++ Mg
2+5700mg/L.
As can be seen from the data in above-described embodiment table 1, polymkeric substance of the present invention has excellent high tackifying, normal salt sensitivity (meet salt retrogradation), the positive Thermo-sensitive (intensification retrogradation) of certain limit and anti-aging, anti-shear ability under high temperature and high salt condition.
Claims (10)
1. be applicable to a polymkeric substance mobility control agent for special high salinity reservoirs, the molecular weight of described polymkeric substance is between 200-2000 ten thousand, and the solution be made up of following monomer or auxiliary agent reacts obtained under the existence of composite initiator; The solution of described monomer composition, with weight parts, comprises following component:
A) nonionic water-soluble monomers of 5 ~ 99.9 parts;
B) 0 ~ 50 part of anionic monomer is or/and cationic monomer;
C) 0.1 ~ 10 part there is surface-active hydrophobic monomer;
D) 0.1 ~ 5 part of inorganics;
E) 1 ~ 20 part of tensio-active agent;
F) water of 200 ~ 2000 parts;
Wherein, described composite initiator, in above-mentioned whole weight percent monomer, comprises following component:
The persulphate of (a) 0.003 ~ 0.5%;
The sulphite of (b) 0.003 ~ 0.5% or bisul-phite;
(c) 0.003 ~ 1% by NR
1r
2r
3representative tertiary amine compounds or by N
+r
4r
5r
6r
7representative quaternary ammonium compounds or by NH
2r
8the fat amine compound of representative, R in formula
1~ R
7all be selected from C
1~ C
14straight or branched alkyl or alkyl derivative, R
8be selected from C
1~ C
18straight or branched alkyl or alkyl derivative;
The azo compound of (d) 0.005 ~ 1%;
The urea of (e) 0.01 ~ 10%, thiocarbamide;
The disodium ethylene diamine tetraacetate of (f) 0.03 ~ 0.5% or diethylene triamine pentacetic acid (DTPA) sodium;
The molecular weight regulator of (g) 0.03 ~ 0.5%;
Described nonionic water-soluble monomers is selected from water-soluble vinyl monomer, and described vinyl monomer is selected from least one in acrylamide, Methacrylamide, NIPA, N-N-DMAA, N-N-acrylamide and N hydroxymethyl acrylamide, N-vinyl formamide, N-vinyl acetamide, N-vinyl pyridine and NVP; Anionic monomer is selected from least one in 2-acrylamide-2-methylpro panesulfonic acid, vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid, fumaric acid, β-crotonic acid, vinylbenzenesulfonic acid, vinyl sulfonic acid, vinyl phosphonate, allyl sulphonic acid, allyl phosphonic acid and/or its water-soluble alkali, alkaline-earth metal and ammonium salt; Cationic monomer is selected from least one in dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and 2-acrylamido-2-trimethoxysilyl propyl methacrylate ammonium chloride; Described inorganics is acidic oxide, basic oxide or intermediate oxide, tensio-active agent be selected from C8-C16 sodium alkyl sulfate, C8-C16 sodium alkyl benzene sulfonate aniorfic surfactant, be selected from the cationic surfactant that C8-C16 alkyl trimethyl bromine (chlorine) changes ammonium, be selected from least one in the non-ionic type of alkylphenol polyoxyethylene (EO=4 ~ 30).
2. the polymkeric substance mobility control agent being applicable to special high salinity reservoirs according to claim 1, having surface-active hydrophobic monomer described in it is characterized in that is anionic surface activity monomer or cationic surfactant monomer.
3. the polymkeric substance mobility control agent being applicable to special high salinity reservoirs according to claim 1, it is characterized in that described acidic oxide is boron oxide, silicon oxide, described basic oxide are barium oxide, manganese oxide, calcium oxide, magnesium oxide, described intermediate oxide position aluminum oxide, zinc oxide.
4. the polymkeric substance mobility control agent being applicable to special high salinity reservoirs according to claim 2, having surface-active hydrophobic monomer described in it is characterized in that is the mono-vinyl compounds being selected from 8-22 carbon atom.
5. the polymkeric substance mobility control agent being applicable to special high salinity reservoirs according to claim 2, is characterized in that described anionic surface activity monomer to be vinyl carbochain number is the acrylamide azanyl sodium sulfonate of 8 ~ 18; Cationic surfactant monomer to be vinyl carbochain number be 12 ~ 22 allyl alkyl ammonium chloride.
6. the polymkeric substance mobility control agent being applicable to special high salinity reservoirs according to claim 1, is characterized in that persulphate is selected from Potassium Persulphate, Sodium Persulfate or ammonium persulphate; Sulphite is selected from S-WAT or potassium sulfite, and bisul-phite is selected from sodium bisulfite or Potassium hydrogen sulfite; Tertiary amine compounds is selected from methacrylic acid N, N-dimethylaminoethyl, vinylformic acid N, N-dimethylaminoethyl, β-dimethylaminopropionitrile, Tetramethyl Ethylene Diamine, vulkacit H; Quaternary ammonium compounds is selected from N, N-dimethyl diallyl ammonium chloride, N, N-diethyl diallyl ammonium chloride; Fat amine compound is selected from methylamine, quadrol, 1,3-propylene diamine, Putriscine, N, N-dimethyl-1,3-propylene diamine; Azo compound is selected from azo diisobutyl amidine hydrochloride, 2,2'-azos [2-(2-tetrahydroglyoxaline-2-base) propane] dihydrochloride; Molecular weight regulator is selected from least one in Virahol, the trimethyl carbinol, isopropylcarbinol, tetramethylolmethane or dipropylene glycol.
7. the preparation method being applicable to the polymkeric substance mobility control agent of special high salinity reservoirs according to claim 1, comprises following step successively:
A () adds water, nonionic water-soluble monomers, anionic monomer in a kettle. or/and cationic monomer, have the auxiliary agents such as surface-active hydrophobic monomer and inorganics;
B () adds the composite initiation system of part, stir, and forms solution;
PH value to 7 ~ 10 of (c) regulator solution, and pass into nitrogen, temperature in the kettle is down to 10 ~ 30 DEG C, then adds remaining composite initiator, after continuing to pass into nitrogen, sealing;
D temperature of reaction was risen to 40 ~ 60 DEG C after 0.5 ~ 1 hour by () gradually, react after 2 ~ 8 hours, obtain gel polymerisate;
E () added the composite hydrolysis agent containing tensio-active agent after cutting glue, 80 ~ 90 oC hydrolysis reaction 2 ~ 4 hours; Then vacuum-drying 3 ~ 6 hours at 60 ~ 90 DEG C, is crushed to certain particle size with pulverizer or rolling machine, obtains the polymkeric substance mobility control agent being applicable to special high salinity reservoirs.
8. the preparation method being applicable to the polymkeric substance mobility control agent of special high salinity reservoirs according to claim 7, is characterized in that, described composite hydrolysis agent, in the whole weight percent monomer of association polymer, comprises following component:
At least one in the sodium hydroxide of (a) 0 ~ 20% or sodium carbonate;
(b) 0.5 ~ 50% tensio-active agent.
9. the preparation method being applicable to the polymkeric substance mobility control agent of special high salinity reservoirs according to claim 8, it is characterized in that, described tensio-active agent is selected from least one in aniorfic surfactant, cationic surfactant, nonionic surface active agent.
10. the preparation method being applicable to the polymkeric substance mobility control agent of special high salinity reservoirs according to claim 9, is characterized in that, described aniorfic surfactant is C
8-16sodium alkyl sulfate, C
8-16sodium alkyl benzene sulfonate; Described cationic surfactant is C
8-16alkyl trimethyl bromine (chlorine) changes ammonium; Non-ionic type is alkylphenol polyoxyethylene (EO=4 ~ 30).
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