CN100587021C - Preparation of shift drive agent of self cross-linked polymer and application method - Google Patents
Preparation of shift drive agent of self cross-linked polymer and application method Download PDFInfo
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- CN100587021C CN100587021C CN200610045359A CN200610045359A CN100587021C CN 100587021 C CN100587021 C CN 100587021C CN 200610045359 A CN200610045359 A CN 200610045359A CN 200610045359 A CN200610045359 A CN 200610045359A CN 100587021 C CN100587021 C CN 100587021C
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Abstract
This invention discloses a method for preparing self-crosslinking polymer profile control agent, which is prepared from acrylamide, cationic monomer DMC, self-crosslinking monomer carboxymethyl acrylamide and water at a weight ratio of (9.07-12.38) : (0.09-0.64) : (2.53-5.29) : (83-86). The method comprises: adding initiator 50 mg/L to the above raw materials at 28-32 deg.C, and copolymerizing for10-13 h. The crosslinking time of self-crosslinking groups and amide groups in the prepared self-crosslinking polymer is adjustable, thus the formed gel can realize profiles control, and has raised sweep coefficient.
Description
One, technical field
The present invention relates to the self-crosslinking polymer transfer drive technological method of raising oil field (particularly oil field behind the polymer flooding) recovery ratio that a kind of suitable oil field deep transfer drive uses, specially refer to the preparation and the application method of shift drive agent of self cross-linked polymer deep adjusting driving agnet, the oil field transfer drive was used after suitable highly aqueous field, polymer flooding exceeded poly-well group and polymer flooding, belonged to the oil development field.
Two, background technology
Development along with oil exploitation technology, especially in recent years improve the oil recovery The application of new technique, in each method of tertiary oil recovery (EOR) that improves recovery ratio, polymer displacement of reservoir oil tech occupies very critical role, therefore, each elephant of China all extensively adopts polymer displacement of reservoir oil tech.2000, China utilized polymer displacement of reservoir oil tech can increase crude production rate more than 1,000 ten thousand tons.
Common polymer flooding agent at present is a polyacrylamide.Polyacrylamide (PAM) and derivative thereof are more important products in the water-soluble displacement of reservoir oil polymkeric substance, extensively apply in the tertiary oil recovery in oil field.But the plain polypropylene acid amides is used for warm high salt and the high temperature and high salt oil deposit displacement of reservoir oil exists shortcomings such as result of use is poor, validity period is short, mainly be under the high temperature and high salinity, the polymkeric substance facile hydrolysis, viscosity reduces, therefore the rheological variation is in use still needed and is further improved.
Invented for this reason and in polyacrylamide, introduced the self-crosslinking group, under formation condition, be cross-linked to form gel, can increase the viscosity of polymkeric substance in salt solution effectively, and the high temperature resistant shear-stable performance of raising polymkeric substance, also can wait the time of controlling the formation gel, to improve the displacement of reservoir oil performance of PAM in tertiary oil recovery by changing self-crosslinking group content and catalyst levels.In addition, in using the oil reservoir of polymer flooding, still leave the polyacrylamide fragment of having degraded in a large number, in this kind oil reservoir, continue to inject self-crosslinking polyacrylamide and catalyzer thereof, can effectively utilize the polyacrylamide in the stratum, reach to reduce and annotate poly-cost, improve the purpose of annotating poly-effect.
Three, summary of the invention
Problem to be solved by this invention is a kind of preparation and application method that can be used for improving the shift drive agent of self cross-linked polymer in highly aqueous field of exploitation; Its distinguishing feature is group and the cation group that has self-crosslinkable in the molecular structure, form the gel except that self carrying out crosslinking reaction, its self-crosslinking group also can form gel (reaction principle is seen accompanying drawing 2) with the amide group generation crosslinking reaction that residues in the partially hydrolyzed polyacrylamide in the stratum, reaches to make full use of the purpose that residues in the polyacrylamide in the stratum.
For achieving the above object, adjusting driving agnet of the present invention is to be generated as the self-cross linking monomer polyreaction by monomers such as N hydroxymethyl acrylamide, acrylamides; The optimization of polymerization process condition such as temperature, reaction times, catalyst levels, proportioning raw materials; Self-crosslinking polymer is cross-linked into glue influence factor (the pH value of reaction system, salinity, catalyst levels, polymer concentration, temperature, water quality etc.).
Transfer drive system involved in the present invention is particularly suitable for highly aqueous Tibetan, poly-driving in back heterogeneous reservoir and poly-the driving goes out to gather the application of oil reservoir transfer drive technology.
The preparation method of described shift drive agent of self cross-linked polymer comprises:
Step 1: the preparation of self-crosslinking polymer: adopt acrylamide and self-cross linking monomer n-methylolacrylamide, cationic monomer methylacryoyloxyethyl trimethyl ammonium chloride to carry out terpolymer.
Step 2: the polymerizing condition of shift drive agent of self cross-linked polymer: 28 ℃-32 ℃ of temperature of reaction, initiator amount 50mg/L, reaction times 10-13 hour;
Step 3: after step 1 and step 2, the shift drive agent of self cross-linked polymer molecular weight that makes reaches 1,100 ten thousand polymkeric substance.Cationic degree 7%～20% adjustable, methylol group content is adjustable at 0.5-5%.
Step 4: the application of shift drive agent of self cross-linked polymer, the shift drive agent of self cross-linked polymer of preparing is mixed with the transfer drive working fluid by design flow with the oil field return water, inject the transfer drive effect of playing by well.
Step 5: the application of shift drive agent of self cross-linked polymer, the working concentration of adjusting driving agnet is 0.8-2% in the described transfer drive working fluid, chromium acetate catalyzer 800-2000mg/L, the gelation time that concentration that can be by adjusting adjusting driving agnet and catalyst concentration control need with become adhesive capacity.
Self-crosslinking polymer
1, DMC-methylacryoyloxyethyl trimethyl ammonium chloride is a kind of cationic monomer, molecular formula:
C
9H
18ClNO
2
2, self-crosslinking polymer adopts acrylamide and self-cross linking monomer carboxymethyl acrylamide, cationic monomer DMC to carry out terpolymer and get.
2.1 raw material
(1) acrylamide (product)
(2) self-cross linking monomer, independently synthetic N-carboxymethyl acrylamide: (reaction times=2.5-3.5 hour, the quality that feeds intake was than acrylamide: formaldehyde: water=39: 47: 64) for pH=10, temperature=50 ℃-52 ℃ for synthesis condition
(3) cationic monomer DMC (product)
2.2 synthesis condition
Ingredient proportion: according to the self-crosslinking polymer product acrylamide is adjusted in the requirement of cationic degree and carboxymethyl content: DMC: the carboxymethyl acrylamide: water=9.07～12.38: 0.09～0.64: 2.53～5.29: 85 (weight ratios)
PH value: 7～7.5
Temperature: 30 ℃
Water quality: deionized water
Pressure: normal pressure
Reaction times: 12 hours
Initiator amount: the 50mg/L initiator is a redox initiator: oxygenant is an ammonium persulphate, consumption 25mg/L: reductive agent is a potassium sulfite, consumption 25mg/L.Initiator generation redox reaction generates free radical, initiated polymerization.
2.3 self-crosslinking polymer product: liquid, self-crosslinking polymer content is 15wt%, molecular weight reaches 1,100 ten thousand, (advantage is can regulate the adsorptive power of self-crosslinking polymer in the stratum and be cross-linked into glue speed to cationic degree 7%～20% adjustable, thereby the control self-crosslinking polymer enters the position on stratum), carboxymethyl content is 0.5-5% adjustable (advantage is the degree of crosslinking that can regulate cross-linked polymer, thereby the viscosity of the gel that control generates)
3, self-crosslinking polymer is cross-linked into the glue Study on influencing factors
The pH value of reaction system, salinity, catalyst levels, polymer concentration, temperature, water quality etc., catalyzer wherein is a transition metal salt, and self-crosslinking polymer and catalyzer is dissolved in the re-injection water, mixes the back and injects the stratum.
The present invention compared with prior art has the following advantages:
The crosslinking time of polymkeric substance self-crosslinking group and amide group is adjustable in the described self-crosslinking polymer, and the gel that is produced can be realized the purpose of deep profile controlling, effectively improves sweep efficiency.Gelation time 2～15 days is adjustable in the transfer drive working fluid, becomes adhesive capacity greater than 5000mPa.s.The gel of this polymer formation is movable gel, can play the effect of the cross-linked polymer displacement of reservoir oil, because this polymkeric substance contains cation group, with sandstone good adhesive capacity is arranged simultaneously, and oil displacement efficiency is improved.Therefore this self-crosslinking polymer integrates the remaining polyacrylamide utilization in stratum, deep profile controlling and the displacement of reservoir oil three big functions, has good usefulness.But the recovery ratio in oil field behind its application economical and effective raising polymer flooding.
Four, description of drawings
No description of drawings.
Five, embodiment
A kind of preparation of shift drive agent of self cross-linked polymer and application method is characterized in that shift drive agent of self cross-linked polymer is to adopt acrylamide and self-cross linking monomer carboxymethyl allylamine, cationic monomer methylacryoyloxyethyl trimethyl ammonium chloride to carry out terpolymer to make; The mass ratio that feeds intake is an acrylamide: the methylacryoyloxyethyl trimethyl ammonium chloride: carboxymethyl acrylamide: water=9.07-12.38: 0.09-0.64: 2.53: 2.53-5.29: 83-86 adds initiator 50mg/L reaction 28 ℃-32 ℃ of temperature and made in 12 hours under normal pressure.
Embodiment 1:
GD1-11-705 injection well profile control rig-site utilization
1, basic overview
In the 11-705 well on March 21st, 2004 metaideophone poly-, the transfer drive working fluid is formulated in and adds mass percent 1% adjusting driving agnet in the sewage, 1500mg/L chromium acetate catalyzer injects water injection well, annotates poly-layer position 52,53+4, changes second slug on October 9th, 2005, by the end of in April, 2006, accumulative total injection of polymer solution 6.6610X104m3, present implantation concentration 2100mg/l, oil pressure 7.10Mpa, day injection allocation 50m3, the real 50m3 that annotates.The injection pressure fluctuation of the poly-back of middle 11-705 metaideophone changes, and the pressure ascensional range is about 1Mpa.
Claims (5)
1, a kind of preparation method of shift drive agent of self cross-linked polymer is characterized in that shift drive agent of self cross-linked polymer is to adopt acrylamide and self-cross linking monomer carboxymethyl acrylamide, cationic monomer methylacryoyloxyethyl trimethyl ammonium chloride to carry out terpolymer to make; The mass ratio that feeds intake is an acrylamide: the methylacryoyloxyethyl trimethyl ammonium chloride: carboxymethyl acrylamide: water=9.07-12.38: 0.09-0.64: 2.53-5.29: 83-86 adds initiator 50mg/L reaction 28 ℃-32 ℃ of temperature and made in 10-13 hour under normal pressure.
2, the preparation method of shift drive agent of self cross-linked polymer according to claim 1, it is characterized in that self-cross linking monomer carboxymethyl acrylamide is by acrylamide: formaldehyde: the mass ratio of water=39: 47: 64, reaction made in 2.5-3.5 hour under 50 ℃ of-52 ℃ of temperature under normal pressure.
3, the preparation method of shift drive agent of self cross-linked polymer according to claim 1 is characterized in that initiator promptly is a redox initiator, and consumption 50mg/L is made up of ammonium persulphate 25mg/L and potassium sulfite 25mg/L.
4, the preparation method of shift drive agent of self cross-linked polymer according to claim 1 is characterized in that the shift drive agent of self cross-linked polymer that will prepare is mixed with the transfer drive working fluid by design flow with oilfield sewage, is injected into the transfer drive oil reservoir by water injection well.
5, the preparation method of shift drive agent of self cross-linked polymer according to claim 4, the working concentration mass percent that it is characterized in that adjusting driving agnet in the transfer drive working fluid is 0.8-2%, chromium acetate catalyzer 800-2000mg/L controls gelation time and becomes adhesive capacity with catalyst concentration by the concentration of adjusting adjusting driving agnet.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101314710B (en) * | 2008-07-18 | 2014-07-09 | 中国石油大学(华东) | Oil displacement profile control agent, displacement of reservoir oil system and displacement of reservoir oil method |
| CN101575966B (en) * | 2009-06-09 | 2013-09-04 | 中国石油天然气股份有限公司 | Method for water plugging and profile controlling of underground polymerization of oil exploitation sludge |
| CN104234676B (en) * | 2014-08-28 | 2017-01-11 | 中国石油天然气股份有限公司 | Method for deep profile control by utilizing ASP (alkaline/surfactant/polymer) combination flooding produced sewage |
| CN104371682A (en) * | 2014-10-20 | 2015-02-25 | 西南石油大学 | AA-AM-AMPS-DAC (acrylic acid-acrylamide-2-acrylamido-methylpropanesulfonic acid-acryloyloxyethyl ammonium chloride) polymer gel plugging agent and synthesis method thereof |
| CN104806195B (en) * | 2015-03-14 | 2017-07-28 | 肖传敏 | A kind of alternative effect thickening thin oil transfer drive method and system |
| CN105837759A (en) * | 2016-03-23 | 2016-08-10 | 重庆科技学院 | Preparation method of cationic core-shell structured microspheres for in-depth profile control |
| CN108504342A (en) * | 2018-04-09 | 2018-09-07 | 王建东 | A kind of preparation method of water shutoff agent |
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Non-Patent Citations (2)
| Title |
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| 甲基丙烯酰氧以及三甲基氯化铵/丙烯酰胺反相乳液的聚合及表征. 李朝艳等.青岛科技大学学报，第26卷第1期. 2005 |
| 甲基丙烯酰氧以及三甲基氯化铵/丙烯酰胺反相乳液的聚合及表征. 李朝艳等.青岛科技大学学报，第26卷第1期. 2005 * |
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