CN102876312A - Acrylamide graft copolymer oil-displacing agent and preparation method thereof - Google Patents
Acrylamide graft copolymer oil-displacing agent and preparation method thereof Download PDFInfo
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- 229920000578 graft copolymer Polymers 0.000 title claims abstract description 37
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 12
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims abstract description 10
- 238000011084 recovery Methods 0.000 claims abstract description 9
- 238000006073 displacement reaction Methods 0.000 claims abstract description 8
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- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 claims 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
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- 239000004160 Ammonium persulphate Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000628997 Flos Species 0.000 description 2
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Abstract
本发明涉及一种丙烯酰胺接枝共聚物驱油剂及制备方法。该聚合物具有水溶性，用量少，表现出较高的增粘性和良好的耐温抗剪切性能。技术方案是：所用原料及单体质量百分比为，质量以克为单位，单体质量百分比为，AM51.5~58.8%，AA40~45.5%，APEG0.1~1.5%，KGM0.1~1.5%。；其制法是，在反应器中先加入KGM，再加入去离子水，在30oC恒温搅拌30min，让其充分溶胀。再依次加入AM、AA和APEG，然后调节pH到6~8，通氮气10min，加入引发剂硝酸铈铵，在35~55oC下反应8h后，将产品经过粗分、精制、干燥、粉碎后，得到聚合物AM/AA/APEG/KGM。0.1wt%的溶液在100oC时的粘度保留率高达91.3%。且该共聚物能够提高模拟原油采收率达11.3%。
The invention relates to an acrylamide graft copolymer oil displacement agent and a preparation method. The polymer is water-soluble, has a small dosage, and exhibits high viscosity-increasing properties and good temperature and shear resistance. The technical solution is: the mass percentage of raw materials and monomers used is gram, the mass percentage of monomer is AM51.5~58.8%, AA40~45.5%, APEG0.1~1.5%, KGM0.1~1.5% . ; The preparation method is to add KGM to the reactor first, then add deionized water, and stir at a constant temperature of 30 o C for 30 minutes to allow it to fully swell. Then add AM, AA and APEG in sequence, then adjust the pH to 6~8, pass nitrogen gas for 10 minutes, add the initiator cerium ammonium nitrate, and react at 35~55 o C for 8 hours, then the product is roughly divided, refined, dried and pulverized Finally, the polymer AM/AA/APEG/KGM was obtained. The viscosity retention rate of 0.1wt% solution at 100 o C is as high as 91.3%. And the copolymer can increase the simulated oil recovery by 11.3%.
Description
Technical field
The present invention relates to a kind of petroleum industry acrylamide grafted copolymer oil-displacing agent and preparation method.
Background technology
Oil is as a kind of important energy and chemical feedstocks, and along with socioeconomic high speed development, people constantly increase the petroleum demand amount.Yet oil is Nonrenewable resources, and its reserves are in continuous minimizing.Yet nearly 60% crude oil can not with conventional oil recovery technique exploitation, directly restrict the development of national economy in the domestic oil reservoir.In order to guarantee the normal need of national economy, it is extremely urgent to improve oil recovery.Therefore in the urgent need to the redevelopment to maturing field, excavate the potentiality of maturing field, stablize the output of oil, tertiary oil recovery (Enhanced Oil Recovery, EOR) is exactly one of method that improves maturing field output, and this technology is many field use at home.At present, the problem that the oil field runs into mainly contains two aspects, is used on the one hand the tertiary oil recovery polymer oil-displacing agent and is mainly polyacrylamide (PAM) and Partially hydrolyzed polyacrylamide (HPAM).Yet PAM or HPAM are at high shear forces, high price mineral ion (Ca
2+, Mg
2+Deng), facile hydrolysis under the condition such as comparatively high temps, degraded, chain be curling etc., cause the solution property cataclysm and do not reach the requirement of engineering construction.Another aspect; polymkeric substance be injected into underground after; will certainly affect underground ecotope; therefore research and develop the special property such as anti-shearing, high temperature resistant, salt tolerant; and favourable to the displacement of reservoir oil at certain phase; but the Eco-friendly polymer oil-displacing agent that finally can be biodegradable again just seems particularly important, must play a part positive to environment protection.
Rhizoma amorphophalli glucomannan (Konjac Glucomannan, be called for short KGM) be aboundresources and macromolecule polysaccharide cheap and easy to get, its main component is that D-Glucose and D-MANNOSE compare with the 1:1.6 amount, by β-1, complex polysaccharide (the Qi Li of 4 glycosidic link combinations, Li Guangji, Zong Minhua. the controlled degradation of enzyme catalysis Rhizoma amorphophalli glucomannan. polymer journal .2003,5:650-654; Liu Yutao, Wang Ziping. the application of Rhizoma amorphophalli glucomannan and progress. West China pharmaceutical journal .2008,23 (2): 188～189).KGM has the multifrequency nature such as wetting ability, gelation, film-forming properties, germ resistance, edibility, low heat value and physiological function that some are special, and therefore domestic have more report at food, medicine, chemical industry and biological field.Wang Yuting etc. are with Fe
2+-H
2O
2For initiator is grafted to acrylonitrile monemer on the cross-linking starch, the Carboxyl-containing Starch that makes can effectively be removed the heavy metal ion (Jianhua XIE in the water body, Pang Jie, Lin Huiqing, Deng. the Rhizoma amorphophalli glucomannan-preparation of carrageenin blend film and performance study pre-test thereof. modern food science and technology, 2007,23 (4): 26-28).Han Huaifen etc. have synthesized Cross-linking Cationic Starch take W-Gum as matrix, to containing Cu
2+, Cd
2+Deng water body have removal effect preferably (Wang Yuting, journey lattice. Carboxyl-containing Starch is removed the research of toxic heavy metal ion in the water body. Environmental Pollution and Control, 1996,18 (2): 16-18).Peng Changhong etc. have synthesized the carboxyl grafting chitosan, and this product can effectively adsorb Pb
2+And Cb
2+Deng (Han Huaifen, Chen Xiaojuan, Jin Mantong. the synthetic and counterweight metal biosorption of Cross-linking Cationic Starch. chemical industry environmental protection, 2005,25 (3): 325-237).Zhang Zhaomin etc. are take Rhizoma amorphophalli glucomannan as raw material, vinyl cyanide is monomer, causing the optimised process that makes the grafting Rhizoma amorphophalli glucomannan by nitric acid berkelium ammonium is: initiator concentration 0.01mol/L, 50 ℃ of monomer concentration 1.6mol/L temperature of reaction, reaction times 3h (Peng Changhong, Wang Yuting, Cheng Ke etc. the synthetic and counterweight metal biosorption performance of carboxyl grafting chitosan. environmental science, 1998,19 (2): 29-33).Abroad to the research of KGM also mainly at medicine, the fields such as food (Miki Y., Tomohisa T., Katsuyoshi N.Effects of Konjac-Glucomannan on the Gelatinization and Retrogradation of Corn Starch As Determined by Rheology and Differential Scanning Calorimetry.J.Agric.Food Chem.1996,44,2970-2976; Gao S.J; Zhang L.N.Molecular Weight Effects on Properties of Polyurethane/Nitrokonjac Glucomannan Semiinterpenetrating Polymer Networks.Macromolecules.2001,34,2202-2207; Mar í a, A.S., Margarita, C., Carmen R.L.et al.Formation of New Glucomannan-Chitosan Nanoparticles and Study of Their Ability To Associate and Deliver Proteins.Macromolecules.2006,39,4152-4158).
Rhizoma amorphophalli glucomannan and some monomer-grafted copolymerization can obtain multiple good characteristic.Therefore, some high polymer monomer is grafted on the natural high moleculer eompound skeleton, makes the grafting polymer compound that makes have both some good characteristic of natural high moleculer eompound and synthetic macromolecular compound, can satisfy the requirement of different application.Given this, we intend take acrylamide as principal monomer, and introducing carboxyl and KGM side group increase the water-soluble of polymkeric substance in the copolymer molecule chain, and introduce long-chain polyether, to improve the anti-shear performance of polymkeric substance.And KGM is natural polymer, and its chain is biodegradable easily, can improve the biodegradability of polymkeric substance.
Summary of the invention
The object of the invention is to: in order to guarantee carrying out smoothly of oil field oil production, the spy provides a kind of acrylamide grafted copolymer oil-displacing agent and preparation method thereof.In order to reach this purpose, the present invention by the following technical solutions:
A kind of acrylamide grafted copolymer oil-displacing agent is by acrylamide code name AM, vinylformic acid code name AA, allyl alcohol polyethenoxy ether code name APEG, the AM/AA/APEG/KGM graft copolymer that four kinds of structural units of Rhizoma amorphophalli glucomannan code name KGM consist of.Its structure is as follows:
In (1) formula, n is the polymerization degree, for greater than 0 integer.
Prepare this acrylamide grafted copolymer oil-displacing agent, comprise following steps, reaction equation is as follows:
The first step: get quantitative KGM in the 150mL there-necked flask, add an amount of water, stir 30min at 30 ℃ of constant temperature, allow its abundant swelling;
Second step: add successively quantitative AM, AA and APEG;
The 3rd step: regulate pH to designated value with 25%NaOH, system is made into the aqueous solution, logical nitrogen 10min;
The 4th step: constant temperature 30min under design temperature, continue to pass into nitrogen 10-20min;
The 5th step: be warming up to temperature required rear constant temperature 20min, add initiator, logical nitrogen 10min at constant temperature lower seal reaction 12h, obtains faint yellow clear, viscous liquid crude product again;
The 6th step: crude product is carried out roughing out and refining, and oven dry is pulverized, and obtains powder-like product AM/AA/APEG/KGM graft copolymer.
The raw materials used proportioning of acrylamide grafted copolymer oil-displacing agent: quality in grams, monomer mass per-cent is, AM 51.5～58.8%, AA40～45.5%, APEG 0.1～1.5%, KGM 0.1～1.5%.The final monomer total mass percentage concentration that is made into is 10～25% aqueous solution.
The final pH scope of system is 6～9 in the 3rd step and the 5th step, and the isothermal reaction temperature is controlled at 35～55 ℃.
Initiator can be chosen a kind of of water miscible hydrogen peroxide, ammonium persulphate, Potassium Persulphate, ceric ammonium nitrate in the 5th step, also can choose the redox system that Potassium Persulphate-sodium bisulfite, ammonium persulphate and sodium bisulfite and ferrous ion and hydrogen peroxide form, preferred ceric ammonium nitrate; The initiator add-on is 0.1～1% of monomer total mass.
Crude product carries out roughing out and refining method is in the 6th step: faint yellow clear, viscous liquid crude product is slowly poured in the beaker that fills dehydrated alcohol and constantly stirred, obtain the white precipitate floss, and soak 5h.Unreacted Rhizoma amorphophalli glucomannan, graft copolymer and autopolymer all are insoluble in the dehydrated alcohol, and filtration under diminished pressure is dried to constant weight under 50 ℃ of conditions, obtain thick product.Again above-mentioned thick product spent glycol-Glacial acetic acid mixed solvent (volume ratio is 2: 3) is soaked 10h, then draw supernatant liquid and repeatedly soak to remove autopolymer and unreacted Rhizoma amorphophalli glucomannan with mixed solvent, obtain the white solid precipitation with absolute ethanol washing at last, under 50 ℃ of conditions, be dried to constant weight, obtain purified product.
The 5th step is when adding initiator in the joining solution, adding be that massfraction is respectively 20% ceric ammonium nitrate solution.
The prepared acrylamide grafted copolymer of the present invention uses in tertiary oil production in oil field as oil-displacing agent.
The present invention has following beneficial effect: (1) has introduced carboxylate groups and poly-hydroxy group in copolymer chain, and it is good water-soluble that polymkeric substance is had; (2) by introducing the huge side group of Rhizoma amorphophalli glucomannan and allyl alcohol polyethenoxy ether chain, make the tackifying ability of polymkeric substance stronger, formed multipolymer consumption on engineering obviously reduces, and can save cost.(3) introducing inside macromole owing to large side group and the hydrophobic long-chain of Soxylat A 25-7, copolymer sheet reveals good heat-resistant salt-resistant and shear resistant.(4) the large side group of the grafting object height molecular structure of making a living is being easier to degraded under the biological action for a long time, therefore less to underground environmental influence.
Description of drawings
Fig. 1 is the infrared spectrum of AM/AA/APEG/KGM graft copolymer.
Fig. 2 is the relation of AM/AA/APEG/KGM graft copolymer solution apparent viscosity and concentration.
Fig. 3 is the apparent viscosity of AM/AA/APEG/KGM graft copolymer solution and the relation of shearing rate.
Fig. 4 is the relation of AM/AA/APEG/KGM graft copolymer solution apparent viscosity and temperature.
Embodiment
The preparation of embodiment 1:AM/AA/APEG/KGM graft copolymer
Get first KGM in the 150mL there-necked flask by the proportioning of table 1 Raw, add the 20ml deionized water, stir 30min at 30 ℃ of constant temperature, allow its abundant swelling.Add successively AM, then AA and APEG regulate pH to designated value with 25%NaOH, system are made into 25% the aqueous solution again, logical nitrogen 10min, be warming up to 40 ℃ after constant temperature 20min, add the initiator ceric ammonium nitrate, logical nitrogen 10min behind 40 ℃ of lower reaction 8h, obtains faint yellow transparent stickiness liquid again.Slowly pour into product in the beaker that fills dehydrated alcohol and constantly stirring, obtain the white precipitate floss, and soak 5h.Unreacted Rhizoma amorphophalli glucomannan, graft copolymer and autopolymer all are insoluble in the dehydrated alcohol, and filtration under diminished pressure is dried to constant weight under 50 ℃ of conditions, obtain thick product.Again above-mentioned thick product spent glycol-Glacial acetic acid mixed solvent (volume ratio is 2: 3) is soaked 10h, then draw supernatant liquid and repeatedly soak to remove autopolymer and unreacted Rhizoma amorphophalli glucomannan with mixed solvent, obtain the white solid precipitation with absolute ethanol washing at last, under 50 ℃ of conditions, be dried to constant weight and pulverizing, obtain the refining graft copolymer product A M/AA/APEG/KGM of powdery.
Table 1 graft copolymer medicine dosage
Embodiment 2:AM/AA/APEG/KGM graft copolymer structure characterizes
The infrared spectrum of the graft copolymer AM/AA/APEG/KGM that synthesizes by embodiment 1 as shown in Figure 1.Show among the figure that the multipolymer INFRARED SPECTRUM is at 3434cm
-1The place produces strong absorption peak, be the stretching vibration of the O-H in the hydroxyl, and peak intensity is more intense, and the existence of poly-hydroxy structure is described; The stretching vibration of N-H is at 3300cm
-1About, because the hydroxyl absorption peak is very strong, N-H is absorbed vibration peak cover, so the N-H absorption peak does not show; At 2938cm
-1The place produces strong absorption peak
2-stretching vibration, at 1677cm
-1Be-stretching vibration of C=O, prove there is amide structure in the polymer molecule that product is the AM/AA/APEG/KGM graft copolymer.
The mensuration of embodiment 3:AM/AA/APEG/KGM graft copolymer relative molecular weight
With reference to GB/T 12005.10-92 " Molecular Weight for Polyacrylamide mensuration viscosimetry ", tetrapolymer with embodiment 2 preparations, be mixed with the solution of 0.1wt%, under 30 ± 0.1 ℃, the intrinsic viscosity that records graft copolymer with dilution method progressively is 1129.3mL/g.Utilize experimental formula M=802[η]
1.25, M is sticking all relative molecular masses, and [η] is intrinsic viscosity, and 802,1.25 are empirical constant.Can be calculated the sticking all relative molecular weight of polymkeric substance and be about 5.3 * 10
6
Embodiment 4:AM/AA/APEG/KGM graft copolymer solution apparent viscosity and concentration relationship are investigated
The AM/AA/APEG/KGM graft copolymer that embodiment 1 is synthesized is made into 0.02～0.1% the aqueous solution, uses Brookfield LVTDV-III viscometers at shearing rate 7.34s under 30 ℃
-1Measure the apparent viscosity of solution under the condition, the result as shown in Figure 2.Can find from Fig. 2: total trend be that the apparent viscosity of polymers soln raises with the increase of the concentration of polymkeric substance.When concentration rises to 0.06wt% from 0.02wt%, apparent viscosity rises to 195mPa.s from 70mPa.s, and concentration rises to 0.1% from 0.06wt%, apparent viscosity but rises to 396mPa.s from 195mPa.s, may be owing within macromole connects, introduce the poly-hydroxy side group, under suitable concentration, the effect of power between a plurality of hydroxyls causes viscosity that larger increasing arranged.In a word, the Efficient Adhesive Promotion of AM/AA/APEG/KGM graft copolymer is obvious, is suitable for doing oil-displacing agent.
The investigation of the embodiment 5:AM/AA/APEG/KGM graft copolymer property sheared
The graft copolymer of embodiment 1 preparation is mixed with the 0.1wt% aqueous solution, is 30 ℃ in temperature, with the HAAKERheoStress6000 rheometer in shearing rate from 170s
-1Rise to 510s
-1, again from 510s
-1Drop to 170s
-1Under the condition, the viscosity of measuring polymers soln changes data such as Fig. 3.Can find from Fig. 3: at constant shearing rate 170s
-1Lower for some time, it is constant that apparent viscosity of polymer is tending towards; When unexpected rising shearing rate arrives 510s
-1The time, apparent viscosity is reduced to 313mPa.s, and this meets the character of superpolymer fluid, when shearing rate is got back to again 170s
-1The time, apparent viscosity almost surely is held in again the apparent viscosity 363mPa.s under the shearing rate of beginning, and the result shows that fully this graft copolymer has obvious viscosity save power under 30 ℃ of high shear rate conditions, and anti-shear performance is better.
Embodiment 6:AM/AA/APEG/KGM graft copolymer temperature tolerance is investigated
Prepared graft copolymer among the embodiment 1 is mixed with 0.1% aqueous solution, is under 33～116 ℃ with the HAAKERheoStress6000 rheometer in temperature, measures the viscosity changing conditions of polymers soln, data such as Fig. 4.Can find from Fig. 4: total trend be that apparent viscosity of polymer rises with temperature, apparent viscosity reduces gradually.When temperature was elevated to 60 ℃, viscosity retention ratio can reach 91.3%, and when temperature rose to 90 ℃ again, viscosity retention ratio was 74.2%, yet when temperature was elevated to 100 ℃, apparent viscosity sharply descended, and viscosity retention ratio is about 63.6%.The result shows that this graft copolymer has preferably viscosity save power below 100 ℃.
The indoor raising recovery ratio of embodiment 7:AM/AA/APEG/KGM graft copolymer (EOR) experiment
It is the 500mg/L aqueous solution that the multipolymer of embodiment 1 preparation is mixed with concentration, and shearing rate is 7.34s
-1The time, apparent viscosity is 158.4mPa.s, total mineralization 7000mg/L (MgCl
21000mg/L, NaCl5000, CaCl
21000mg/L), the simulating oil deposit temperature is 65 ℃; Simulated oil viscosity: 74.6mPas (65 ℃, shearing rate 7.34S
-1), the one dimension sand-packed model: Φ 25x500, water displacing oil: mixed water injection water injects injection rate as 0.3PV with 1mL/min injection speed displacement simulation oil take 1mL/min, the 500mg/L polymers soln, follow-up water 1ml/min, water saturation reaches 98.5%.With compare with doing displacement of reservoir oil laboratory experiment with clear water under the condition, this polymkeric substance improves Simulation of Crude Oil recovery ratio can reach 11.3%.
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