CN103320109A - Novel quaternary copolymerization phosphate clay stabilizer and synthetic method thereof - Google Patents
Novel quaternary copolymerization phosphate clay stabilizer and synthetic method thereof Download PDFInfo
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- CN103320109A CN103320109A CN2013102584135A CN201310258413A CN103320109A CN 103320109 A CN103320109 A CN 103320109A CN 2013102584135 A CN2013102584135 A CN 2013102584135A CN 201310258413 A CN201310258413 A CN 201310258413A CN 103320109 A CN103320109 A CN 103320109A
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Abstract
The invention discloses a novel quaternary copolymerization phosphate clay stabilizer and a synthetic method. The synthetic method comprises the following steps of: (1) placing a hydrophobic monomer, a phosphate monomer, alkylphenol ethoxylates, acrylamide and acrylic acid into a three-necked flask, adding distilled water, and stirring till dissolution; (2) regulating the pH value of a solution obtained from the step (1) by using a NaOH solution; (3) installing a nitrogen guide pipe in a reactor at room temperature, and accessing N2 for 30 minutes; (4) adding an initiating agent ammonium persulfate ((NH4)2S2O8), sodium bisulfite (NaHSO3), carrying out thermostatic reaction for a period of time, and then continuously reacting for 8 hours to obtain a corresponding polymer. According to the invention, a water-soluble polymer clay stabilizer for inhibiting clays from being hydrated and expanded in oil field development is synthesized.
Description
Technical field
The present invention relates to a kind of quarternary copolymerized phosphoric acid salt and synthetic method thereof for the petroleum industry clay stabilizer.
Technical background
Continuous exploratory development along with the oil field; protection to reservoir is more and more important; clay mineral extensively is present in the oil reservoir; if do not take on stream adequate measures; will cause the hydration swelling of clay mineral and disperse migration; stop up hole, shout, reduce rate of permeation, the infringement reservoir.In order to alleviate the infringement to reservoir, must use the clay mineral in the chemical processing agent good ground.
At present, the clay stabilizer of producing both at home and abroad and using can be divided into four class (J.Swenson, M.V.Smalley, H.L.M.Hatharasinghe, et al.Interlayer Structure of a Clay-Polymer-Salt-Water System.Langmuir[J] .2001,17 (13): 3813 – 3818; Chen Zhimin. the synthetic Research Advances in Evaluation [J] that reaches of clay stabilizer. chemical engineering and equipment .2009,8:130-150).(1) inorganic salts: as: KCl, NaCl, CaCl
2Deng.This class clay stabilizer price is low, working service is simple, but resistance to erosion not, and can not produce multipoint adsorption (E.S.Boek, P, V, Coveney, N.T.Skipper.Monte Carlo Molecular Modeling Studies of Hydrated Li
+, Na
+, and K
+Smectites:Understanding the Role of Potassium as a Clay Swelling Inhibitor[J] .J.Am.Chem.Soc., 1995,117 (50): 12608 – 12617; Liu Xiangjun, Yuan Shulong, Liu Hong, Wu Xiaolin. solution salinity and dosage are on the impact research [J] of sodium-montmorillonite intergranular distance. rock-soil mechanics .2011,32 (1): 137-140).(2) cats product: its advantage is that adsorption is strong, but water resistant flushing, shortcoming is to make reservoir become lipophilicity, reduce the relative permeability (JhonK.Borchardt of oil gas phase, Duncan, Okla.Methods of minimizing fines migration in subterranean formations.US4536304,1985 (02)).(3) organic cationic polymer: mainly take quaternary and polyquaternium type clay stabilizer as main; this class clay stabilizer use range is wide; stabilising effect is good; working lipe is long; the hydration swelling that can suppress clay can be controlled again the dispersion migration of particulate; and the rinse capability of antiacid, alkali, oil, water is all stronger; as: poly-trimethylallylammonium chloride (PTMAAC) (Feng Li; poplar is solemn; Wang Ge. the intercalation home position polymerization reaction [J] of quaternary ammonium salt monomer in polynite. SCI .2006,11:2213-2216).(4) amphoteric ion polymer class clay stabilizer: its temperature resistant antisalt performance is good, suppress the hydration and expansion of clay ability strong, more and more be subject to each major field developer's extensive concern (Liu Yan, Bi Kai, Guo Liang etc. synthetic and the performance evaluation [J] of new type amphoteric ion clay stabilizer. chemistry and biotechnology .2011,28 (6): 53-55).
In recent years, research is found: the C-P key in the organophosphate is more firm than P-O-P, the C-O-P key of inorganic phosphate, thereby organic phosphoric acid has higher chemical stability, and the ability of good high temperature resistance, phosphate group is incorporated in the polymer molecular chain, help to increase the heat-resistant salt-resistant ability (Gou Shaohua of multipolymer, Gou Guangjun, Ye Zhongbin. the phosphatic synthetic and performance study [J] of a kind of terpolymer. chemical research and application, 2011,23 (8): 998-1000).Meanwhile, introduce the long-chain hydrophobic grouping at molecular chain, can increase the anti-shear ability (Li Meirong of polymkeric substance, Liu Zhi, Cao Xulong etc. hydrophobic association type polyacrylamide (HAPAM) and conventional polyacrylamide (HPAM) increase glutinous mechanism. petroleum journal, 2012,28 (6): 1037-1042).Based on this, we propose the 3-dimethylin allyl group phosphoric acid of the synthetic a kind of C-P of the containing bond structure of meter and contain the N-allyl group amine hydroxybenzene of long-chain hydrophobic grouping, prepare a kind of novel clay soil stablizer with vinylformic acid, acrylamide copolymerization.
Summary of the invention
The object of the invention is to: have good temperature resistant antisalt, anti-shear ability in order to make polymkeric substance, can suppress preferably the hydration swelling of clay, the spy provides a kind of phosphoric acid salt multipolymer and synthetic method thereof.
In order to achieve the above object, the present invention has adopted technical scheme: a kind of quadripolymer, this polymkeric substance comprises the tetrapolymer of acrylamide (code name AM), vinylformic acid (code name AA), N-allyl group amine hydroxybenzene (code name NAO), 3-dimethylin allyl group phosphoric acid (code name DMAAPA) formation, and its structure is as follows:
Wherein, m, n, p, q are the polymerization degree, and infrared spectrum is seen Fig. 2; Raw materials used per-cent is (quality in grams) AM69.65%, AA30.00%, NAO0.20%, DMAAPA0.150%.
This synthetic polymer method is: add first 0.0150g DMAAPA and 0.0200g NAO in the 250mL three-necked flask, add again 6.9650g AM, 3.0000g AA, 0.0035g emulsifier op-10 and 1.665g NaOH, be configured to monomer total mass percentage concentration and be 10%～20% the aqueous solution, pass into N
230min; Then add initiator ammonium persulfate solution and sodium sulfite solution, its mol ratio is 1:1, and the initiator add-on is monomer total mass 0.5%, continues to pass into N
210min～20min reacts 8h under 45 ° of C of temperature; Use at last absolute ethanol washing three times, pulverize, oven dry makes the AA/AM/DMAAPA/NAO quadripolymer.
The application of this polymkeric substance is: measure anti-swollen rate according to China National Petroleum industry standard SY/T5971294 water filling with shale expansion instrument in the clay stabilizer method of evaluating performance, above-mentioned quadripolymer is mixed with the aqueous solution that concentration is 6000ppm, uses intelligent high-temperature high-voltage shale expansion instrument to measure the respectively expansion height in pure water and polymers soln of 5g na montmorillonite.By calculating, draw this quadripolymer solution and can reach 78.20% to the anti-swollen rate of na montmorillonite with this understanding.Same solution is when composite with finite concentration KCl, and anti-swollen rate reaches 95.43%; Composite with other inorganic salt, and prevent swollen test all obtaining preferably preventive effect of expansion.
The present invention has following beneficial effect: (1) introduces phosphate group and hydroxy-acid group in molecular chain, and the water-soluble of polymer molecular chain strengthened greatly; (2) introduce the long-chain hydrophobic grouping at polymer molecular chain, make polymkeric substance show preferably saline-alkaline tolerance and anti-shear ability.(3) this polymkeric substance shows good heat resistance, can suppress preferably the hydration swelling of clay.
Description of drawings
Fig. 1: the molecular structure of AA/AM/DMAAPA/NAO tetrapolymer of the present invention;
Fig. 2: the infrared spectrogram of AA/AM/DMAAPA/NAO tetrapolymer of the present invention;
Fig. 3: the apparent viscosity of AA/AM/DMAAPA/NAO tetrapolymer solution of the present invention and the relation of temperature;
Fig. 4: the apparent viscosity of AA/AM/DMAAPA/NAO tetrapolymer solution of the present invention and the relation of shearing rate;
Fig. 5: the apparent viscosity of AA/AM/DMAAPA/NAO tetrapolymer solution of the present invention and the relation of NaCl concentration;
Fig. 6: apparent viscosity and the CaCl of AA/AM/DMAAPA/NAO tetrapolymer solution of the present invention
2Relation.
Embodiment
Embodiment 1: tetrapolymer AA/AM/DMAAPA/NAO's is synthetic
The proportioning of pressing table 1 adds 0.0150g DMAAPA and 0.0200g NAO in the 250mL three-necked flask, add again 6.9650g AM, 3.0000g AA, 0.0035g emulsifier op-10 and 1.6650g NaOH, be configured to monomer total mass percentage concentration and be 10%～20% the aqueous solution, pass into N
230min; Then add initiator ammonium persulfate solution and sodium sulfite solution, its mol ratio is 1:1, and the initiator add-on is monomer total mass 0.1%～0.5%, continues to pass into N
210min～20min is to react 8h under 30 ° of C～60 ° C in temperature; Use at last absolute ethanol washing three times, pulverize, oven dry makes this quadripolymer.
The medicine dosage that table 1 tetrapolymer is synthetic
Embodiment 2: the structural characterization of tetrapolymer AA/AM/DMAAPA/NAO
The infrared spectrum of the tetrapolymer AA/AM/DMAAPA/NAO that synthesizes by embodiment 1 is shown in 2.As we know from the figure, at 3422.70cm
-1There is stronger amino stretching vibration absorption peak at the place, at 3185.22cm
-1The place is the absorption peak of imino-, 1656cm
-1The place is the absorption peak of carbonyl, 1101.11cm
-1The place is the absorption peak of the two keys of phosphorus oxygen.
Embodiment 3: tetrapolymer AA/AM/DMAAPA/NAO temperature resistance is investigated
The sample that embodiment 1 is synthesized carries out the temperature resistance investigation.The tetrapolymer that makes is mixed with the aqueous solution of 2000ppm,, under ° C condition of 30 ° of C～120, measures the aqueous solutions of polymers apparent viscosity and change data such as Fig. 3 in temperature.Can find from Fig. 3, polymkeric substance is along with the rising of temperature, and apparent viscosity reduces gradually.When temperature was elevated to 120 ° of C, apparent viscosity of polymer was 36.0mPas, and viscosity retention ratio reaches 34.6%.The result shows that this polymkeric substance has preferably heat resistance.
Embodiment 4: tetrapolymer AA/AM/DMAAPA/NAO shear resistant is investigated
The sample that embodiment 1 is synthesized carries out the shear resistant investigation.The tetrapolymer that makes being mixed with the aqueous solution of 2000ppm, is 35 ° of C in temperature, shearing rate 7.34s
-1～1000s
-1Under the condition, measure the apparent viscosity changing conditions of polymers soln, data such as Fig. 4.Can find from Fig. 4: apparent viscosity of polymer rises with shearing rate, and apparent viscosity reduces gradually.When shearing rate is elevated to 1000s
-1The time, apparent viscosity of polymer is 40.3mPas, viscosity retention ratio reaches 17.7%.The result shows that this polymkeric substance is 1000s in 35 ° of C, shearing rate
-1Has obvious viscosity save power under the condition.
Embodiment 5: tetrapolymer AA/AM/DMAAPA/NAO salt resistance is investigated
The above-mentioned tetrapolymer that makes is mixed with the aqueous solution of 2000ppm, at certain NaCl, CaCl
2Measure its apparent viscosity under the concentration conditions, shown in Fig. 4,5.As can be seen from Figure 4, when NaCl concentration was 12000ppm, the apparent viscosity of polymers soln was 145mPas, and viscosity retention ratio is 21.3%; As can be seen from Figure 5, work as CaCl
2When concentration was 1000ppm, the apparent viscosity of polymers soln was 140mPas, and viscosity retention ratio is 20.6%.Show that this polymkeric substance has certain anti-salt property.
Embodiment 6: tetrapolymer AA/AM/DMAAPA/NAO prevents swollen property laboratory experiment
Measure anti-swollen rate according to China National Petroleum industry standard SY/T5971294 water filling with shale expansion instrument in the clay stabilizer method of evaluating performance, above-mentioned quadripolymer is mixed with the aqueous solution that concentration is 6000ppm, use intelligent high-temperature high-voltage shale expansion instrument NP-3 type to measure the respectively expansion height in pure water and polymer clay stabiliser solution of 5g na montmorillonite, calculate as can be known: anti-swollen rate is 78.20%.When concentration is that polymers soln and the different inorganic salt of 6000ppm carry out when composite, anti-swollen experimental result is as follows:
The anti-swollen experiment that table 2 polymers soln and inorganic salt are composite
Can find out, when aqueous solutions of polymers and the different inorganic salt of 6000ppm are composite, all obtain preferably preventive effect of expansion, when wherein composite with KCl, anti-swollen rate is the highest.
Claims (6)
1. the synthetic method of quarternary copolymerized phosphoric acid salt clay stabilizer is characterized in that, comprises following step:
(1) with hydrophobic monomer N-allyl group amine hydroxybenzene (code name NAO), phosphoric acid salt 3-dimethylin allyl group phosphoric acid (code name DMAAPA) and alkylphenol polyoxyethylene (OP-10), acrylamide (AM), vinylformic acid (AA) place there-necked flask, add distilled water and are stirred to dissolving;
(2) use the afterwards pH value of solution of NaOH solution regulating step (1);
(3) under the room temperature, in reactor, load onto and lead nitrogen tube, pass into N
230min;
(4) add initiator ammonium persulfate ((NH
4)
2S
2O
8), sodium bisulfite (NaHSO
3), isothermal reaction for some time.
2. the synthetic method of quarternary copolymerized phosphoric acid salt clay stabilizer according to claim 1 is characterized in that, described reactor is there-necked flask.
3. the synthetic method of quarternary copolymerized phosphoric acid salt clay stabilizer according to claim 1 is characterized in that, the method for described step method (2) is: regulate about pH value to 7 with NaOH solution.
4. the synthetic method of quarternary copolymerized phosphoric acid salt clay stabilizer according to claim 1 is characterized in that, adds (NH in the method for described step (4)
4)
2S
2O
8, NaHSO
3N is led in rear continuation
2And stirring 10min～20min.
5. the synthetic method of quarternary copolymerized phosphoric acid salt clay stabilizer according to claim 1 is characterized in that, the steady temperature of water-bath is 45 ° of C in the described step (4).
6. the synthetic method of quarternary copolymerized phosphoric acid salt clay stabilizer according to claim 1 is characterized in that, isothermal reaction 8h in the described step (4).
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| CN105837749A (en) * | 2016-04-07 | 2016-08-10 | 西南石油大学 | A retardant and a retardant acid working solution |
| CN115819655A (en) * | 2021-09-17 | 2023-03-21 | 中国石油化工股份有限公司 | Underground self-synthesis shrinkage-expansion agent and preparation method thereof |
| CN116063626A (en) * | 2021-10-30 | 2023-05-05 | 中国石油化工股份有限公司 | Anti-calcium shrinkage and expansion agent and preparation method and application thereof |
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| CN115819655A (en) * | 2021-09-17 | 2023-03-21 | 中国石油化工股份有限公司 | Underground self-synthesis shrinkage-expansion agent and preparation method thereof |
| CN115819655B (en) * | 2021-09-17 | 2023-09-01 | 中国石油化工股份有限公司 | Underground self-synthesis swelling shrinking agent and preparation method thereof |
| CN116063626A (en) * | 2021-10-30 | 2023-05-05 | 中国石油化工股份有限公司 | Anti-calcium shrinkage and expansion agent and preparation method and application thereof |
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Application publication date: 20130925 |