CN103320113B - A kind of water-soluble AM-AA-NVP-BEMA tetrapolymer oil-displacing agent and synthetic method thereof - Google Patents
A kind of water-soluble AM-AA-NVP-BEMA tetrapolymer oil-displacing agent and synthetic method thereof Download PDFInfo
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- CN103320113B CN103320113B CN201310260153.5A CN201310260153A CN103320113B CN 103320113 B CN103320113 B CN 103320113B CN 201310260153 A CN201310260153 A CN 201310260153A CN 103320113 B CN103320113 B CN 103320113B
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Abstract
The invention discloses a kind of water-soluble AM-AA-NVP-BEMA tetrapolymer oil-displacing agent and synthetic method thereof, this oil-displacing agent is the tetrapolymer be made up of acrylamide (AM), vinylformic acid (AA), NVP (NVP), function monomer (BEMA); Raw materials used mass percent is: acrylamide 60%-70%, vinylformic acid 29.8%-38.5%, NVP 0.1%-1.0%, function monomer (BEMA) 0.1%-0.5%.Its synthetic method is: first in there-necked flask, add function monomer (BEMA), NVP, vinylformic acid, acrylamide, be 7.0-7.5 by sodium hydroxide solution adjust ph, add distilled water and be made into the aqueous solution that monomer total mass concentration is about 20%; After the temperature of solution to be mixed reaches 40 DEG C, add ammonium persulfate-sodium bisulfite initiator, logical N
2protection, reacts 6h at temperature is 40 DEG C; Tetrapolymer is obtained through absolute ethanol washing, oven dry, pulverizing.Oil-displacing agent of the present invention has good heatproof, salt tolerant and anti-shear performance.
Description
Technical field
The present invention relates to oilfield polymer flooding technical field, particularly one water-soluble AM-AA-NVP-BEMA tetrapolymer oil-displacing agent and synthetic method thereof.
Background technology
Polymer flooding adds a certain amount of water-soluble polymers at injection water, plays by the viscosity and reduction rate of permeation improving injection water the effect controlling mobility, expand swept volume and raising oil recovery factor.At present, polymer flooding has entered industrialization phase in the oil field such as grand celebration, triumph, huge port, Jilin, Henan of China, wherein the polymer flooding of Daqing oil field is polymer injection project maximum in the world, and the yearly rate-oil production of this oilfield polymer flooding is more than 1,000 ten thousand tons.
At present, the polymkeric substance that polymer flooding uses is mainly polyacrylamide (PAM) or partially hydrolyzed polyacrylamide (HPAM), these polymkeric substance good oil increasing effect can be obtained for when low temperature, low mineralization oil reservoir, but significantly reducing for its oil increasing effect during high temperature and high salinity oil reservoir.In addition, polymkeric substance can be subject to the violent shearing action of injection pump, pipeline, perf and immediate vicinity of wellbore etc. in injection process, and the viscosity of polymers soln will significantly reduce, and the effect of polymer flooding also will be subject to serious impact.Therefore, while the heat-resistant salt-resistant performance improving Polymer Used For Oil Displacement, the anti-shear performance strengthening polymkeric substance is also needed.
The present invention is prepared the function monomer (DAMA) with reactive behavior by 1,3-propylene diamine and maleic anhydride, be introduced in polymkeric substance and polymer molecule can be made to have certain spacial framework, thus improves the anti-shear performance of polymkeric substance; In addition, introducing has the NVP of five-membered ring structure in order to improve the heat resistance of polymkeric substance in the polymer.
Summary of the invention
The object of the invention is: in order to improve the Oil Displacing Capacity of polymkeric substance under high temperature, high salinity and high discharge capacity injection condition, spy provides a kind of water-soluble AM-AA-NVP-BEMA tetrapolymer oil-displacing agent and synthetic method thereof.
The technical scheme that the present invention takes for its technical problem of solution is: a kind of water-soluble AM-AA-NVP-BEMA tetrapolymer oil-displacing agent, this oil-displacing agent is the tetrapolymer be made up of function monomer (BEMA), NVP, acrylamide, vinylformic acid, and its structural formula is as follows:
AM-AA-NVP-BEMA
In formula, l, m, n, p, q, x, y, z are the polymerization degree, and infrared spectra is shown in Fig. 1; The mass percent of raw materials used monomer is: acrylamide 60%-70%, vinylformic acid 29.8%-38.5%, NVP 0.1%-1.0%, and function monomer (BEMA) 0.1%-0.5%, quality in grams.
The synthetic method of this oil-displacing agent is: first in 100mL there-necked flask, add 0.02g function monomer (BEMA), 0.03g NVP, 6.25g AM and 3.70g AA, be 7.0-7.5 by sodium hydroxide solution adjust ph, be made into the aqueous solution that monomer total mass concentration is 20%; Add initiator ammonium persulfate solution and sodium sulfite solution (mol ratio is 1:1) again, initiator add-on is 0.5% of monomer total mass, continues to pass into nitrogen, under temperature is 40 DEG C of conditions, react 8h; Tetrapolymer can be obtained through washing with alcohol, oven dry, pulverizing.
The method for making of function monomer (BEMA) is: in 100mL round-bottomed flask, add 9.9g maleic anhydride and 20mL dehydrated alcohol, stirs and makes it dissolve; In round-bottomed flask, slowly drip 3.7g1, the mixing solutions of 3-propylene diamine and 20mL dehydrated alcohol, after dropping completely, at 30 DEG C, react 5h; Filter reaction product, and use a large amount of distilled water wash, finally dry at 60 DEG C and obtain function monomer (BEMA).
The application of this oil-displacing agent is: preparation mass concentration is the AM-AA-NVP-BEMA tetrapolymer aqueous solution (NaCl concentration is 5000mg/L) of 2000mg/L.By one dimension sand-packed model after saturation water more saturated crude oil (be 7.34s in shearing rate
-1, temperature be viscosity under 60 DEG C of conditions is 35.8mPa.s); Use the oil in the NaCl solution displacement one dimension sand-packed model of 5000mg/L again, until water ratio reaches 98%; Finally use the remaining oil in the aqueous copolymers solution displacement one dimension sand-packed model of 2000mg/L, until water ratio reaches again reach 98%.Improve recovery ratio 26.06% from the oil displacement experiment result known 2000mg/L AM-AA-NVP-BEMA aqueous solution, show and improve recovery ratio ability preferably.
The present invention has following beneficial effect: (1) is by 1, after 3-propylene diamine and maleic anhydride react, connect polymerisable double bond at 1,3-propylene diamine two ends, and can be polymerized with vinylformic acid and acrylamide, the tetrapolymer synthesized has certain spacial framework; (2) this oil-displacing agent has higher viscosity at high shear rates, has stronger anti-shear ability, may be used for oilfield polymer flooding.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of AM-AA-NVP-BEMA of the present invention;
Fig. 2 is the anti-shear ability of AM-AA-NVP-BEMA of the present invention;
Fig. 3 is the temperature resistant capability of AM-AA-NVP-BEMA of the present invention;
Fig. 4 is the saline-alkaline tolerance of AM-AA-NVP-BEMA of the present invention;
Fig. 5 is the raising recovery ratio ability of AM-AA-NVP-BEMA of the present invention.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is described in further detail.Should be appreciated that specific embodiment described herein only in order to explain the present invention, and be not used in restriction invention.
Embodiment 1: the synthesis of function monomer (BEMA)
In 100mL round-bottomed flask, add 9.9g maleic anhydride and 20mL dehydrated alcohol, stir and make it dissolve; In round-bottomed flask, slowly drip 3.7g1, the mixing solutions of 3-propylene diamine and 20mL dehydrated alcohol, after dropping completely, at 30 DEG C, react 5h; Filter reaction product, and use a large amount of distilled water wash, finally dry at 60 DEG C and obtain function monomer (BEMA).
Embodiment 2: the synthesis of water-soluble AM-AA-NVP-BEMA tetrapolymer
First in 100mL there-necked flask, add 0.02g function monomer (BEMA), 0.03g NVP, 6.25g AM and 3.70g AA, be 7.0-7.5 by sodium hydroxide solution adjust ph, be made into the aqueous solution that monomer total mass concentration is 20%; Add initiator ammonium persulfate solution and sodium sulfite solution (mol ratio is 1:1) again, initiator add-on is 0.5% of monomer total mass, continues to pass into nitrogen, under temperature is 40 DEG C of conditions, react 8h; Tetrapolymer can be obtained through washing with alcohol, oven dry, pulverizing.
Embodiment 3: the sign of water-soluble AM-AA-NVP-BEMA tetrapolymer
By the infrared spectrogram of the water-soluble AM-AA-NVP-BEMA tetrapolymer of the 2-in-1 one-tenth of embodiment as shown in Figure 1, N-H stretching vibration absorption peak is positioned at 3422.53cm
-1;-CH
2stretching vibration absorption peak is positioned at 2931.04cm
-1; C=O stretching vibration absorption peak is positioned at 1675.22cm
-1;-NH flexural vibration absorption peak (in face) absorption peak is positioned at 1554.93cm
-1; C-N stretching vibration absorption peak is positioned at 1400.32cm
-1;-NH flexural vibration absorption peak (outside face) absorption peak is positioned at 663.67cm
-1; The charateristic avsorption band of NVP is positioned at 1456.74cm
-1.
Embodiment 4: the anti-shear performance of water-soluble AM-AA-NVP-BEMA tetrapolymer
Above-mentioned obtained water-soluble AM-AA-NVP-BEMA tetrapolymer distilled water is mixed with the aqueous solution that mass concentration is 2000mg/L, by its viscosity under different shear rate of rheometer measurement at 60 DEG C.As shown in Figure 2, the AM-AA-NVP-BEMA of 2000mg/L is at 500s
-1viscosity retention ratio after down cut 5min is 83.58%.
Embodiment 5: the heat resistance of water-soluble AM-AA-NVP-BEMA tetrapolymer
Be the aqueous solution of 2000mg/L by above-mentioned obtained water-soluble AM-AA-NVP-BEMA tetrapolymer distilled water compound concentration, with Brookfiled DV-III viscometer, (shearing rate is 7.34s
-1) measure aqueous solutions of polymers apparent viscosity at different temperatures.As can be seen from Figure 3, the apparent viscosity of 2000mg/L AM-AA-NVP-BEMA solution declines along with the rising of temperature, and at 95 DEG C, the apparent viscosity of solution is 105.1mPa.s, and this multipolymer has good heat resistance.
Embodiment 6: the salt resistant character of water-soluble AM-AA-NVP-BEMA tetrapolymer
Be the copolymer solution of 2000mg/L by above-mentioned obtained water-soluble AM-AA-NVP-BEMA tetrapolymer distilled water compound concentration, respectively to the NaCl adding different mass in the copolymer solution of 2000mg/L, stirring makes it dissolve completely, and with Brookfiled DV-III viscometer, (shearing rate is 7.34s
-1) measure the viscosity of copolymer solution at 60 DEG C.As can be seen from Figure 4, along with NaCl concentration raises, the apparent viscosity of multipolymer reduces rapidly, tends towards stability subsequently.When NaCl concentration is 18000mg/L, the apparent viscosity of aqueous copolymers solution is 35.9mPa.s, and this copolymer sheet reveals stronger anti-salt property.
Embodiment 7: the oil-displacement capacity of water-soluble AM-AA-NVP-BEMA tetrapolymer
Preparation mass concentration is the AM-AA-NVP-BEMA tetrapolymer aqueous solution (NaCl mass concentration is 5000mg/L) of 2000mg/L.Adopt the oil-displacement capacity of one dimension sand-packed model research copolymer solution, test and carry out at 60 DEG C.The internal diameter of one dimension sand-packed model is 2.5cm, and length is 50cm, middle filling quartz sand (rate of permeation: 534 × 10
-3μm
2, porosity: 23.2%).The step of oil displacement experiment is as follows: (1) saturation water: the NaCl salt solution injecting 5000mg/L with the speed of 0.5mL/min in one dimension sand-packed model; (2) saturated oil: make the saturated crude oil of one dimension sand-packed model (at 60 DEG C, viscosity is for 35.8mPa.s), until the exit end of one dimension sand-packed model only has crude oil to flow out with the speed of 0.1mL/min, 0.2mL/min and 0.3mL/min respectively; (3) water displacing oil: use the NaCl solution of 5000mg/L with the crude oil in the speed displacement one dimension sand-packed model of 0.5mL/min, until water ratio reaches 98%; (4) injection of polymer: the polymers soln (with 5000mg/L NaCl saline) injecting 0.35PV (volume of voids) 2000mg/L with the speed of 0.5mL/min to one dimension sand-packed model; (5) sequent water flooding: use the NaCl solution of 5000mg/L with the crude oil in the speed displacement one dimension sand-packed model of 0.5mL/min, until water ratio reaches 98% again.As can be seen from Figure 5, the recovery ratio in water displacing oil stage is that 33.14%, the 2000mg/L AM-AA-NVP-BEMA aqueous solution improves recovery ratio 26.06%, shows stronger raising recovery ratio ability.
Claims (1)
1. a water-soluble AM-AA-NVP-BEMA tetrapolymer oil-displacing agent, is characterized in that, this oil-displacing agent is obtained by reacting by acrylamide AM, vinylformic acid AA, NVP NVP, function monomer BEMA tetra-kinds of structural units; The structural formula of AM-AA-NVP-BEMA tetrapolymer is as follows:
AM-AA-NVP-BEMA tetrapolymer oil-displacing agent, its synthetic method is, first in 100mL there-necked flask, add 0.02g function monomer BEMA, 0.03gNVP, 6.25gAM and 3.70gAA, be 7.0-7.5 by sodium hydroxide solution adjust ph, be made into the aqueous solution that monomer total mass concentration is 20%; Add initiator ammonium persulfate solution and sodium sulfite solution that mol ratio is 1:1 again, initiator add-on is 0.5% of monomer total mass, passes into nitrogen, under temperature is 40 DEG C of conditions, react 8h; Tetrapolymer can be obtained through washing with alcohol, oven dry, pulverizing;
BEMA monomer, its synthetic method is, adds 9.9g maleic anhydride and 20mL dehydrated alcohol in 100mL round-bottomed flask, stirs and makes it dissolve; In round-bottomed flask, slowly drip 3.7g1, the mixing solutions of 3-propylene diamine and 20mL dehydrated alcohol, after dropping completely, at 30 DEG C, react 5h; Filter reaction product, and use a large amount of distilled water wash, finally dry at 60 DEG C and obtain function monomer BEMA.
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| CN102031101A (en) * | 2009-09-25 | 2011-04-27 | 中国石油化工股份有限公司 | Heat-resistant and salt-resistant polymer thickening agent and preparation method thereof |
| CN102372820A (en) * | 2010-08-26 | 2012-03-14 | 中国石油化工股份有限公司 | Long branched chain polymer used for tertiary oil recovery and synthesis method thereof |
| CN102627957A (en) * | 2012-03-22 | 2012-08-08 | 西南石油大学 | Pyridine ring-containing polymer oil displacement agent and preparation method thereof |
| CN102757358A (en) * | 2012-07-10 | 2012-10-31 | 陕西科技大学 | Ethylenedimaleamic acid and preparation method thereof |
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| CN102031101A (en) * | 2009-09-25 | 2011-04-27 | 中国石油化工股份有限公司 | Heat-resistant and salt-resistant polymer thickening agent and preparation method thereof |
| CN102372820A (en) * | 2010-08-26 | 2012-03-14 | 中国石油化工股份有限公司 | Long branched chain polymer used for tertiary oil recovery and synthesis method thereof |
| CN102627957A (en) * | 2012-03-22 | 2012-08-08 | 西南石油大学 | Pyridine ring-containing polymer oil displacement agent and preparation method thereof |
| CN102757358A (en) * | 2012-07-10 | 2012-10-31 | 陕西科技大学 | Ethylenedimaleamic acid and preparation method thereof |
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