CN103320111B - A kind of AM/AA/NVP/YEML quadripolymer oil-displacing agent and synthetic method thereof - Google Patents
A kind of AM/AA/NVP/YEML quadripolymer oil-displacing agent and synthetic method thereof Download PDFInfo
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- CN103320111B CN103320111B CN201310253549.7A CN201310253549A CN103320111B CN 103320111 B CN103320111 B CN 103320111B CN 201310253549 A CN201310253549 A CN 201310253549A CN 103320111 B CN103320111 B CN 103320111B
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Abstract
The present invention relates to a kind of polymer flooding and improve oil recovery factor AM/AA/NVP/YEML quadripolymer oil-displacing agent and synthetic method thereof.Its technical scheme is: the quadripolymer that the function monomer (YEML) that this oil-displacing agent is prepared by acrylamide AM, vinylformic acid AA, NVP (NVP), quadrol and maleic anhydride is formed; Raw materials used composition is AM63.5%-70%, AA28.7%-36%, NVP0.1%-0.2%, YEML0.1%-0.2%.Its synthetic method is first in flask, add obtained YEML monomer, then add AM, NVP, vinylformic acid and NaOH, is made into the solution that monomer total mass concentration is 10%-20%, and logical nitrogen 30min, then adds initiator, continues logical N
210-20min, reacts 4-12h at temperature 30-60 DEG C; Finally obtain AM/AA/NVP/YEML quadripolymer with absolute ethanol washing, pulverizing, oven dry.The viscosity of Inventive polymers and heat-resistant salt-resistant, shear resistant a larger increase, can improve oil recovery factor preferably, exploit for crude oil.
Description
Technical field
The present invention relates to a kind of polymer flooding and improve oil recovery factor technical field, a kind of AM/AA/NVP/YEML quadripolymer oil-displacing agent of special design and synthetic method thereof.
Background technology
The polyacrylamide PAM of high molecular and partial hydrolysis polyacrylamide HPAM is the most frequently used polymkeric substance in oil field, but PAM and HPAM of high molecular viscosity retention ratio under the high shear forces of pumping and pipe stream is low.And in Oil Field use procedure, after linear PAM and HPAM is subject to shearing action, the molecular chain of polymkeric substance will be destroyed, and the viscosity of polymkeric substance and the Adsorption And Retention ability in porous medium be reduced, thus cause the mobility control ability of polymkeric substance to reduce.Meanwhile, under higher reservoir temperature, HPAM facile hydrolysis and degraded make the viscosity of HPAM sharply decline, and do not reach the requirement of engineering construction, thus have impact on widely using of PAM and HPAM.
At home and abroad, mainly to improve the temperature resistant antisalt performance of polymkeric substance to the mode of acrylamide copolymer or chemical modification by introducing heatproof, salt resistant function type monomer.At present, the non-linear polymer such as star polymer, branched polymer and branch-shape polymer have received increasing concern.Meanwhile, these non-linear polymers such as grade are introduced thermal resisting anti-salt type function monomer as NVP (NVP), 2-acrylamide-2-methyl propane sulfonic (AMPS), sodium allyl sulfonate (SAS) and the function monomer 3-acrylamido-3 Methylbutanoic acid sodium etc. of complexing divalent-metal ion can significantly can improve heat and salt resistance and the shear resistant of polymkeric substance.
Therefore, for the defect of HPAM class heat and salt resistance difference, we will improve its weak point from the following aspect: (1) improves the thermostability of main polymer chain, by adding the ring texture of rigidity while introducing dendritic function monomer; (2) introduce special functional group, suppress or reduce hydrolysis and the degraded of HPAM base polymer to a certain extent.
Summary of the invention
The object of the invention is to: in order to make polymkeric substance have good heat-resistant salt-resistant and shear stability, can improve oil recovery factor preferably, spy provides a kind of novel polymeric oil-displacing agent and synthetic method thereof.
In order to reach above object, the present invention is by the following technical solutions: a kind of novel polymeric oil-displacing agent, this polymer oil-displacing agent comprises the AM/AA/NVP/YEML quadripolymer of acrylamide code name AM, vinylformic acid code name AA, modified function monomer code name YEML, NVP code name NVP tetra-kinds of structural units formations, and its structural formula is as follows:
In formula, x, y, z, a, b, l, m, n are the polymerization degree, and infrared spectrum is shown in Fig. 1; Raw materials used monomer mass percentage ratio is, quality in grams, AM63.5%-70%, AA28.7%-36%, NVP0.1%-0.2%, YEML0.1%-0.2%
The synthetic method of modified function monomer: add 4.2g maleic anhydride and 20mL ethanol in 100mL round-bottomed flask, stirring and dissolving is complete; In round-bottomed flask, slowly drip the mixing solutions of 2mL quadrol and 20mL ethanol, after dropping completely, at 50 DEG C, react 4h; Filter reaction product, and use a large amount of deionized water wash, finally at 60 DEG C, obtain modified function monomer YEML after bake drying.
The synthetic method of this novel polymeric oil-displacing agent: first add the above-mentioned obtained YEML of 0.0100g in 250mL three-necked bottle, add 6.5000gAM, 3.4700gAA, 1.9085g sodium hydroxide and 0.0200g NVP again, being mixed with monomer total mass percentage concentration is the aqueous solution of 10%-20%, logical nitrogen 30min; Then add initiator ammonium persulfate solution and sodium sulfite solution, ammonium persulphate and sodium bisulfite mol ratio are 1:1, and initiator add-on is the 0.1%-0.5% of monomer total mass, continue logical N
210-20min, reacts 4-12h at temperature 30-60 DEG C; Finally obtain AM/AA/NVP/YEML quadripolymer with absolute ethanol washing, pulverizing, oven dry.
The application of this polymer oil-displacing agent is: it is 1500ppm solution that above-mentioned obtained quadripolymer is mixed with concentration, and shearing rate is 7.34s
-1time, apparent viscosity is 254.8mPa.s, and total mineralization is 8000ppm, simulating oil deposit temperature 70 C; Simulated oil viscosity 107.8mPa.s, one dimension sand-packed model (diameter 25mm, length 500mm), water displacing oil; First with 1mlL/min saturation simulation local water, then with 1ml/min saturation simulation oil; Again with 1mL/min water displacing oil, until water ratio reaches 98%, reinject 1500mg/L polymers soln 0.3PV, continues sequent water flooding, until water ratio reaches 98%.The simulation of this polymkeric substance improves oil recovery factor can reach more than 17.7%.
The invention has the beneficial effects as follows: the NVP introduced in (1) polymkeric substance, the rigidity of polymer molecular chain is strengthened greatly, viscosity and the heat-resistant salt-resistant performance of polymkeric substance significantly improve; (2) use sodium acrylate copolymerization, introduce carboxylate groups, make the water-soluble increase of polymkeric substance; (3) this polymers exhibit goes out good heat-resistant salt-resistant and shear resistant, can improve oil recovery factor preferably, exploits for crude oil.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of AM/AA/NVP/YEML quadripolymer of the present invention.
Fig. 2 is the apparent viscosity of AM/AA/NVP/YEML quadripolymer solution of the present invention and the relation of shearing rate.
Fig. 3 is the apparent viscosity of AM/AA/NVP/YEML quadripolymer solution of the present invention and the relation of temperature.
Fig. 4 is the apparent viscosity of AM/AA/NVP/YEML quadripolymer solution of the present invention and the relation of additional inorganic salt concentration.
Fig. 5 is that AM/AA/NVP/YEML quadripolymer lab simulation of the present invention improves recovery ratio (EOR) figure.
Embodiment
The preparation of embodiment 1:YEML monomer
In 100mL round-bottomed flask, add 4.2g maleic anhydride and 20mL ethanol, stirring and dissolving is complete; In round-bottomed flask, slowly drip the mixing solutions of 2mL quadrol and 20mL ethanol, after dropping completely, at 50 DEG C, react 4h; Filter reaction product, and use a large amount of deionized water wash, finally at 60 DEG C, obtain modified function monomer YEML after bake drying.
Embodiment 2: the synthesis of quadripolymer AM/AA/NVP/YEML
First in 250mL three-necked bottle, the above-mentioned obtained YEML of 0.0100g is added by the proportioning of table 1, add 6.5000gAM, 3.4700gAA, 1.9085g sodium hydroxide and 0.0200g NVP again, being mixed with monomer total mass percentage concentration is the aqueous solution of 10%-20%, logical nitrogen 30min; Then add initiator ammonium persulfate solution and sodium sulfite solution, ammonium persulphate and sodium bisulfite mol ratio are 1:1, and initiator add-on is the 0.1%-0.5% of monomer total mass, continue logical N
210-20min, reacts 4-12h at temperature 30-60 DEG C; Finally obtain AM/AA/NVP/YEML quadripolymer with absolute ethanol washing, pulverizing, oven dry.
Table 1 quadripolymer synthetic drug dosage
| Medicine | Dosage/g |
| AM | 6.5000 |
| AA | 3.4700 |
| NVP | 0.0200 |
| YEML | 0.0100 |
| NaOH | 1.9085 |
| NaHSO 3 | 0.0314 |
| (NH 4) 2S 2O 8 | 0.0687 |
| Distilled water | 40.000 |
Embodiment 3:AM/NaAA/NVP/YEML quadripolymer structural characterization
By the infrared spectrum of quadripolymer AM/AA/NVP/YEML that goes out synthesized by embodiment 2 as shown in Figure 1; From figure ,-C (O) NH
2stretching vibration peak be positioned at 3413.8cm
-1, the stretching vibration peak of-C=O is positioned at 1667.7cm
-1; In primary amide and secondary amide, C-N stretching vibration is respectively at 1387.9cm
-1and 1309.7cm
-1there is stronger absorption peak, on NVP ring
with C-N stretching vibration respectively at 1169.9cm
-1and 1100cm
-1.
The embodiment 4:AM/AA/NVP/YEML quadripolymer property sheared is investigated
Above-mentioned obtained novel polymeric oil-displacing agent is mixed with mass concentration, the aqueous solution of 5000mg/L, by its viscosity under different shear rate of rheometer measurement at 30 DEG C, as shown in Figure 2, in shearing rate lower than 50s
-1time, along with the increase of shearing rate, the viscosity degradation amplitude of the aqueous solution is larger; In shearing rate higher than 50s
-1time, along with the increase of shearing rate, the viscosity degradation amplitude of solution is less, and viscosity retention ratio is higher.
Embodiment 5:AM/AA/NVP/YEML quadripolymer temperature tolerance is investigated
Above-mentioned obtained novel polymeric oil-displacing agent is mixed with the aqueous solution that mass concentration is 5000mg/L, and by its viscosity at different temperatures of Brookfiled viscometer determining, shearing rate is 7.34s
-1, as shown in Figure 3, the viscosity of the aqueous solution declines along with the rising of temperature, and the viscosity when temperature is 90 DEG C is 1200mPa.s, shows good heat resistance.
Embodiment 6:AM/AA/NVP/YEML quadripolymer salt resistance is investigated
Preparation mass concentration is the AM/AA/NVP/YEML quadripolymer oil-displacing agent aqueous solution of 5000mg/L, a certain amount of NaCl is added respectively in this aqueous solution a certain amount of, make the NaCl containing different concns in the aqueous solution, use its viscosity at 30 DEG C of Brookfiled viscometer determining again, shearing rate is 7.34s
-1, as shown in Figure 4, the viscosity of the aqueous solution declines along with the rising of NaCl concentration, and the viscosity when salinity is 20000mg/L is 756.8mPa.s.
Embodiment 7:AM/AA/NVP/YEML quadripolymer improves recovery ratio (EOR) laboratory experiment
Above-mentioned obtained oil-displacing agent is mixed with the aqueous solution that mass concentration is 1500mg/L; This aqueous solution is injected into one dimension sand-packed model (sand-packed model internal diameter 25mm, length is 500mm), original is 72% containing saturation ratio, and water drive to water ratio is 98%, crude oil used temperature be 70 DEG C, shearing rate is 7.34s
-1viscosity under condition is 107.8mPa.s) in, rate of injection is 1mL/min, and after this oil-displacing agent aqueous solution of injection 0.3PV, continuing water drive to water ratio is 98%, and the amplitude that this oil-displacing agent improves recovery ratio is 17.7%.
Claims (2)
1. an AM/AA/NVP/YEML quadripolymer oil-displacing agent, is characterized in that: this polymer oil-displacing agent is obtained by reacting by acrylamide code name AM, vinylformic acid code name AA, modified function monomer code name YEML, NVP code name NVP tetra-kinds of structural units;
AM/AA/NVP/YEML quadripolymer, its structural formula is as follows:
AM/AA/NVP/YEML quadripolymer oil-displacing agent, its synthetic method is, in 250mL three-necked bottle, first add the YEML that 0.0100g is obtained, add 6.5000gAM, 3.4700gAA, 1.9085g sodium hydroxide and 0.0200gNVP again, being mixed with monomer total mass percentage concentration is the aqueous solution of 10%-20%, logical nitrogen 30min; Then 1:1 adds initiator ammonium persulfate solution and sodium sulfite solution in molar ratio, and initiator add-on is the 0.1%-0.5% of monomer total mass, continues logical N
210-20min, reacts 4-12h at temperature 30-60 DEG C; Finally obtain AM/AA/NVP/YEML quadripolymer with absolute ethanol washing, pulverizing, oven dry;
YEML monomer, its synthetic method is, in 100mL round-bottomed flask, add 4.2g maleic anhydride and 20mL ethanol, stirring and dissolving is complete; In round-bottomed flask, slowly drip the mixing solutions of 2mL quadrol and 20mL ethanol, after dropping completely, at 50 DEG C, react 4h; Filter reaction product, and use a large amount of deionized water wash, finally at 60 DEG C, obtain modified function monomer YEML after bake drying.
2. the application of polymer oil-displacing agent according to claim 1, is characterized in that: obtained quadripolymer being mixed with concentration is the 1500ppm aqueous solution, and shearing rate is 7.34s
-1time, apparent viscosity is 254.8mPas, and total mineralization is 8000ppm, simulating oil deposit temperature 70 C; Simulated oil viscosity 107.8mPas, one dimension sand-packed model diameter 25mm, length 500mm, water displacing oil; With oily with 1mL/min saturation simulation after 1mL/min saturation simulation local water; Again with 1mL/min water displacing oil, until water ratio reaches 98%, reinject 1500mg/L polymers soln 0.3PV, continues sequent water flooding, until water ratio reaches 98%, the simulation of this polymkeric substance improves oil recovery factor can reach more than 17.7%.
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| CN112341570B (en) * | 2020-11-28 | 2022-08-26 | 西安石油大学 | Double-aqueous-phase polyacrylamide terpolymer nano microsphere emulsion and preparation method thereof |
| CN113234191B (en) * | 2021-06-08 | 2022-11-29 | 中石化南京化工研究院有限公司 | Temperature-resistant salt-resistant cationic polyacrylamide and preparation method thereof |
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| 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 |
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| 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 |
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