CN103087701B - AM (Acrylic Amide)/NaAA (Sodium Acrylate)/AOC (Allyl Para Toluene Sulfonamide) ternary polymer oil-displacing agent and synthetic method thereof - Google Patents
AM (Acrylic Amide)/NaAA (Sodium Acrylate)/AOC (Allyl Para Toluene Sulfonamide) ternary polymer oil-displacing agent and synthetic method thereof Download PDFInfo
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Abstract
The invention provides an AM (Acrylic Amide)/NaAA (Sodium Acrylate)/AOC (Allyl Para Toluene Sulfonamide) ternary polymer oil-displacing agent and a synthetic method thereof. The AM/NaAA/AOC ternary polymer oil-displacing agent comprises the following materials in percentage by weight: 51.1%-53.6% of AM, 46.4%-48.9% of NaAA and 0.2%-1.2% of AOC. The synthetic method comprises the following steps of: adding AOC and emulsifier OP-10 to a three-necked flask; then adding AM, AA (Acrylic Acid) and NaOH to the three-necked flask to prepare an aqueous solution with mass percentage concentration of 10%-20%; and introducing nitrogen gas to the aqueous solution, then adding ammonium persulfate solution and sodium hydrogen sulfite solution in sequence, enabling the mixture to react for 4 hours to 12 hours at 40 DEG C to 50 DEG C to prepare the AM/NaAA/AOC ternary polymer. The polymer is good in water solubility, heat resistance and salt resistance, and capable of indoors improving the oil production rate of the simulated oil to 9%.
Description
Technical field
The present invention relates to tertiary oil recovery displacement of reservoir oil field, particularly polymer oil-displacing agent and synthetic method thereof.
Background technology
The water-soluble polymers that is used for the oil field displacement of reservoir oil mainly comprises take acrylic amide as main synthetic polymer, Natural and Modified Natural Materials and biological polymer.But Natural and Modified Natural Materials poor heat stability, biological polymer cost is high, thereby its application is restricted.The polymkeric substance that the partially hydrolyzed polyacrylamide (HPAM) of take is at present representative is applied widely in tertiary oil recovery, but when applying at the scene, this base polymer also there are some problems: the HPAM of high molecular weight dissolves difficulty, and easily shear degradation; HPAM is easily hydrolyzed under comparatively high temps, and temperature resistant antisalt is poor, has had a strong impact on polymer flooding and at high temperature, high salinity reservoirs was, has improved the effect of recovery ratio.In order to meet the needs of high temperature, the high salinity reservoir displacement of reservoir oil, the development of thermal resisting anti-salt type water-soluble polymers becomes the hot subject of domestic and international polymer oil-displacing agent research.
Nineteen eighty-three, the people such as F.D.Martin, for the shortcoming of partially hydrolyzed polyacrylamide (HPAM), synthesize the acrylamide polymer of two kinds of modifications, compare with HPAM, demonstrate better properties, are mainly in salt solution, still to retain higher viscosity.Moradi-Araghi in 1987, the people such as A be take acrylamide (AM), 2-acrylamide-2-methylpro panesulfonic acid sodium (NaAMPS) and are synthesized AM/NaAMPS multipolymer as raw material, result shows, AM/NaAMPS multipolymer has good heatproof and anti-salt property.Calendar year 2001, the people such as G.OYahaya are incorporated into the monomer that contains phenyl ring in polymer chain, synthesized acrylamide N-benzylacrylamide multipolymer, and aqueous solutions of polymers is carried out to performance evaluation, found that this polymkeric substance has certain tackify saline-alkaline tolerance.The people such as Luo Kaifu in 1999 adopt free radical aqueous solution copolymerization legal system standby water miscible acrylamide/(2-methacryloyl-oxygen ethyl dimethyl dodecyl bromination ammonium (AM/MEDMDA) multipolymer has been studied the solution property of multipolymer.Result shows, compares with partially hydrolyzed polyacrylamide, and this product has excellent salt resistance.2004, the people such as Luo Guiming adopted acrylamide (AM), N-dodecyl acrylamide (C
12aM) and 2-acrylamido-2-dodecyl ethyl sulfonic acid (AMC
14s) synthesized used for tertiary oil recovery polymer P L-2, experimental result shows: this polymer flooding agent PL-2 has good Efficient Adhesive Promotion and shear resistant thermostability.2006, the people such as Liao Li adopt 3-acrylamido-3 Methylbutanoic acid sodium (NaAMB) and 2-acrylamide-2-methylpro panesulfonic acid (AMPS), acrylamide (AM) to synthesize AM/AMPS/NaAMB terpolymer, result shows that this polymkeric substance has good anti-salt property and thickening property, but temperature resistance DeGrain, is further improved.
Sulfamide compound is compared with general amides and is difficult to hydrolysis, in tolysulfonyl amine structure, contain phenyl ring, be introduced in polymkeric substance, can effectively improve polymkeric substance chain rigidity, and the lone-pair electron in toluol sulfonamide on nitrogen-atoms can with complexing of metal ion, thereby increase the stability of polymkeric substance, salt-resistant temperature.Due to the hydrophobic interaction of allyl group tolysulfonyl amine groups and static, hydrogen bond or van der Waals interaction, in intermolecular automatic generation, there is some strength but reversible physics associates again, thereby form huge 3 D stereo mesh space structure, polymer viscosified effect is increased.Based on above thinking, make allyl group para toluene sulfonamide and wide material sources, a kind of novel AM/NaAA/AOC ter-polymers oil-displacing agent of acrylamide, sodium acrylate copolymerization cheap and easy to get.
Summary of the invention
The object of the invention is to: AM/NaAA/AOC ter-polymers oil-displacing agent and synthetic method thereof are provided, by improving tackifying ability, the temperature resistant antisalt of polymkeric substance, its oil displacement efficiency when high temperature, high salinity reservoirs was are used are improved.
Product technology scheme of the present invention is:
AM/NaAA/AOC ter-polymers oil-displacing agent is to consist of acrylamide AM, sodium acrylate NaAA, tri-kinds of monomers of allyl group para toluene sulfonamide AOC, and its structural formula is:
In formula, h is mass percent 51.1 ~ 53.6%, and m is mass percent 46.4 ~ 48.9%, and n is mass percent 0.2% ~ 1.2%, and infrared spectrum is shown in Fig. 1.The synthetic method of monomer A OC: add 3.81g para toluene sulfonamide and 10mL methylene dichloride in 100mL single port flask, under condition of ice bath, slowly drip the mixed solution of 1.37g allyl amine, 2.02g triethylamine and 5mL methylene dichloride, after reaction 5 ~ 7h, use respectively deionized water, dilute hydrochloric acid, dilute sodium hydroxide and saturated common salt water washing, and dry filter, underpressure distillation obtains faint yellow solid AOC.Reaction equation is as follows:
The invention provides the synthetic method of AM/NaAA/AOC ter-polymers oil-displacing agent:
The first step, adds the above-mentioned allyl group para toluene sulfonamide of 0.02g and 0.02g emulsifier op-10 at 250mL three-necked flask; Add a small amount of distilled water to be stirred to solution transparent;
Second step, adds 5.0g acrylamide, 5.0g vinylformic acid, then adds a certain amount of deionized water that it is dissolved, and with NaOH solution, regulating pH is 7, is made into monomer total mass percentage concentration 20% aqueous solution, 45 ° of C of steady temperature, logical nitrogen 20min;
The 3rd step, adds initiator ammonium persulfate solution and sodium sulfite solution, and ammonium persulphate and sodium bisulfite mol ratio are 1:1, and initiator add-on is 0.3% of monomer total mass, continues to pass into nitrogen 10 ~ 20min, under 45 ° of C of temperature, reacts 4 ~ 12h;
The 4th step, uses absolute ethanol washing three times, pulverizes, and dries, and makes AM/NaAA/AOC ter-polymers.
The application of this polymer oil-displacing agent is:
The present invention has the following advantages: the existence of (1) carboxylate groups, has polymkeric substance better water-soluble; (2) introducing of benzsulfamide group, makes the rigidity of polymer molecular chain greatly strengthen and improve the problem of its facile hydrolysis, and the viscosity of polymkeric substance increases greatly, and thermostability and salt resistance improve; (3) above-mentioned polymkeric substance is used as Flooding Agent for EOR, lab simulation oil displacement efficiency is remarkable, can obviously improve recovery ratio.
Accompanying drawing explanation
The infrared spectrum of Fig. 1 AM/NaAA/AOC ter-polymers of the present invention.
The Electronic Speculum microtexture of Fig. 2 AM/NaAA/AOC ternary polymer solution of the present invention.
The relation of Fig. 3 AM/NaAA/AOC ternary polymer solution of the present invention apparent viscosity and temperature.
The relation of Fig. 4 AM/NaAA/AOC ternary polymer solution of the present invention apparent viscosity and NaCl concentration.
Fig. 5 AM/NaAA/AOC ternary polymer solution of the present invention apparent viscosity and CaCl
2the relation of concentration.
Fig. 6 AM/NaAA/AOC ternary polymer solution of the present invention apparent viscosity and MgCl
2the relation of concentration.
Embodiment
The preparation of embodiment 1:AOC monomer
The synthetic method of the synthetic method of AOC monomer: monomer A OC: add 3.81g para toluene sulfonamide and 10mL methylene dichloride in 100mL single port flask, under condition of ice bath, slowly drip the mixed solution of 1.37g allyl amine, 2.02g triethylamine and 5mL methylene dichloride, after reaction 5 ~ 7h, use respectively deionized water, dilute hydrochloric acid, dilute sodium hydroxide and saturated common salt water washing, and dry filter, underpressure distillation obtains faint yellow solid AOC.
Synthesizing of embodiment 2:AM/NaAA/AOC ter-polymers
By the proportioning of table 1, first take AOC, OP-10 in 250mL three-necked flask, add a small amount of distilled water to be stirred to solution transparent, add again AM and AA, after room temperature is dissolved it completely, with NaOH solution, regulate pH to 7, logical nitrogen 20min, add pre-assigned sodium sulfite solution, stir 5min, then add ammonium persulfate solution, continue logical nitrogen 10min, at 45 ° of C lower seal reaction 8h of constant temperature.By absolute ethanol washing, precipitation, precipitated powder is broken into particle, with being dried and making AM/NaAA/AOC ter-polymers after soaked in absolute ethyl alcohol under 40 ° of C.
The synthetic drug dosage of table 1AM/NaAA/AOC ter-polymers
Embodiment 3:AM/NaAA/AOC ter-polymers structural characterization
The monomer A OC going out by embodiment 2 synthesizeds and the infrared spectrum of ter-polymers AM/NaAA/AOC are as shown in Figure 1.In polymkeric substance spectrogram, learn ， – OH and-NH
2stretching vibration peak at 3428.09cm
-1, 3254.18cm
-1place, peak broadens ， – C=O stretching vibration peak at 1690.63cm
-1place, 1314.38cm
-1, 1112.0cm
-1place is-SO
2-characteristic peak, 1546.82cm
-1, 879.60cm
-1place is the characteristic peak of phenyl ring.
Embodiment 4:AM/NaAA/AOC terpolymer temperature tolerance is investigated
Prepared polymer formulation in embodiment 2 is become to the 0.2wt% aqueous solution, and when temperature is 30 ° of C, its apparent viscosity is 542.4mPas.Constant temperature 10min under design temperature, uses Brook field D-III+Pro viscometer at 7.34s respectively
-1survey its apparent viscosity.Data are as Fig. 3.Polymers soln apparent viscosity rises with temperature, and reduces gradually.When temperature is elevated to 90 ° of C, viscosity is 333.4mPas, and viscosity retention ratio is 61.5%.
Embodiment 5:AM/NaAA/AOC ter-polymers salt resistance is investigated
Prepared polymkeric substance in embodiment 2 be take to deionized water and be mixed with the 0.1wt% aqueous solution as solvent, initial viscosity is 352.6mPas.Get respectively 100mL polymers soln, add the NaCl of 1.2wt%, the CaCl of 0.12wt%
2and MgCl
2, use Brook field D-III+Pro viscometer at 7.34s
-1survey its apparent viscosity.Data are as shown in Fig. 4, Fig. 5, Fig. 6.When NaCl concentration reaches 12000mg/L, its viscosity retention ratio reaches 32.1%; Work as CaCl
2and MgCl
2when concentration reaches 1200mg/L, its viscosity retention ratio reaches respectively 30.2%, 31.7%.Compare with the anti-salt of polyacrylamide, this polymkeric substance has obvious anti-salt property.
Embodiment 6:AM/NaAA/AOC ter-polymers Oil Displacing Capacity is investigated
Above-mentioned ter-polymers AM/NaAA/ACO is mixed with to the aqueous solution that concentration is 2000ppm, and shearing rate is 7.34s
-1, apparent viscosity is 660.5mPas, total mineralization is 8000mg/L, 65 ° of C of simulating oil deposit temperature; Simulated oil viscosity 70.34mPa.s, one dimension sand-packed model, Φ 25 * 500, water displacing oil; Mixed water injection water is oily with 1mL/min injection speed displacement simulation, the injection speed 1mL/min of this polymers soln, and concentration is 2000ppm, injection rate is 0.3PV, follow-up water 1mL/min, water saturation reaches 98.5%.This polymkeric substance simulation improves oil recovery factor and can reach 9%.
Claims (3)
1.AM/NaAA/AOC ter-polymers oil-displacing agent, is characterized in that: this polymer oil-displacing agent comprises acrylamide AM, sodium acrylate NaAA, tri-kinds of monomers of allyl group para toluene sulfonamide AOC, and the synthetic method of described polymer oil-displacing agent is:
The first step, adds the above-mentioned allyl group para toluene sulfonamide of 0.02g and 0.02g emulsifier op-10 at 250mL three-necked flask, adds a small amount of distilled water to be stirred to solution transparent;
Second step, adds 5.0g acrylamide, 5.0g vinylformic acid and a certain amount of deionized water that it is dissolved, and with NaOH solution, regulating pH is 7, is made into monomer total mass percentage concentration 20% aqueous solution, 45 ℃ of steady temperatures, logical nitrogen 20min;
The 3rd step, adds initiator ammonium persulfate solution and sodium sulfite solution, and ammonium persulphate and sodium bisulfite mol ratio are 1:1, and initiator add-on is 0.3% of monomer total mass, continues to pass into nitrogen 10～20min, under temperature 45 C, reacts 4～12h;
The 4th step, uses absolute ethanol washing three times, pulverizes, and dries, and makes AM/NaAA/AOC ter-polymers.
2. a polymer oil-displacing agent as claimed in claim 1, the synthetic method of contained monomer A OC wherein, it is characterized in that: in 100mL single port flask, add 3.81g para toluene sulfonamide and 10mL methylene dichloride, under condition of ice bath, slowly drip the mixed solution of 1.37g allyl amine, 2.02g triethylamine and 5mL methylene dichloride, after reaction 5～7h, use respectively deionized water, dilute hydrochloric acid, dilute sodium hydroxide and saturated common salt water washing, and dry filter, underpressure distillation obtains faint yellow solid AOC.
3. polymer oil-displacing agent according to claim 1, is characterized in that: above-mentioned ter-polymers AM/NaAA/AOC is mixed with to the aqueous solution that concentration is 2000ppm, and shearing rate is 7.34s
-1, apparent viscosity is 660.5mPas, total mineralization is 8000mg/L, 65 ℃ of simulating oil deposit temperature; Simulated oil viscosity 70.34mPa.s, one dimension sand-packed model, Φ 25 * 500, water displacing oil; Mixed water injection water is oily with 1mL/min injection speed displacement simulation, the injection speed 1mL/min of this polymers soln, and concentration is 2000ppm, injection rate is 0.3PV, follow-up water 1mL/min, water saturation reaches 98.5%, and this polymkeric substance simulation improves oil recovery factor and can reach 9%.
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| 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 |
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| 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 |
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