CN102876312B - 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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Abstract
The invention relates to an acrylamide graft copolymer oil-displacing agent and a preparation method thereof. The acrylamide graft copolymer oil-displacing agent is water-soluble, is low in using amount and has relatively high thickening property and good temperature resistance and shear resistance. The invention adopts the technical scheme as follows: the acrylamide graft copolymer oil-displacing agent comprises the following raw materials and monomers in mass percentages: with gram as a mass unit, 51.5-58.8% of AM (acrylamide), 40-45.5% of AA (acrylic acid), 0.1-1.5% of APEG (allyl polyethylene glycol ether) and 0.1-1.5% of KGM (konjac glucomannan). The preparation method of the acrylamide graft copolymer oil-displacing agent comprises the following steps: adding the KGM into a reactor, adding deionized water, and stirring for 30 minutes at the constant temperature of 30 DEG C so as to sufficiently swell the obtained mixture; sequentially adding the AM, the AA and the APEG; regulating PH to 6-8, inflating nitrogen for 10 minutes, and adding an initiator ceric ammonium nitrate; and reacting for 8 hours at 35-55 DEG C, and roughly separating, refining, drying and pulverizing a product to obtain a polymer AM/ AA /APEG/ KGM. The viscosity retaining rate of a 0.1wt% solution of the acrylamide graft copolymer oil-displacing agent at 100 DEG C is as high as 91.3%; and the acrylamide graft copolymer oil-displacing agent can improve the recovery factor of simulation crude oil 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 petroleum demand amount.But oil is Nonrenewable resources, its reserves are in continuous minimizing.But in domestic oil reservoir, the crude oil of nearly 60% can not be exploited with conventional oil recovery technique, directly governs the development of national economy.In order to ensure the normal need of national economy, improve oil recovery extremely urgent.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) be exactly one of method improving maturing field output, this technology is many field use at home.At present, the problem that oil field runs into mainly contains two aspects, is used for the polyacrylamide (HPAM) that tertiary oil recovery polymer oil-displacing agent is mainly polyacrylamide (PAM) and partial hydrolysis on the one hand.But PAM or HPAM is 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 solution property cataclysm and do not reach the requirement of engineering construction.Another aspect; polymkeric substance is after being injected into underground; the ecotope of underground will certainly be affected; therefore the special propertys such as anti-shearing, high temperature resistant, salt tolerant are researched and developed; and it is 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 1:1.6 amount, by β-1, complex polysaccharide (the Qi Li that 4 glycosidic links combine, 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 multifrequency nature and some special physiological functions such as wetting ability, gelation, film-forming properties, germ resistance, edibility, low heat value, and therefore domestic have more report at food, medicine, chemical industry and biological field.Wang Yuting etc. are with Fe
2+-H
2o
2for acrylonitrile monemer is grafted on cross-linking starch by initiator, obtained Carboxyl-containing Starch effectively can remove the heavy metal ion (Jianhua XIE in water body, Pang Jie, Lin Huiqing, Deng. Rhizoma amorphophalli glucomannan-carrageenin blend film preparation and performance study pre-test thereof. modern food science and technology, 2007,23 (4): 26-28).Han Huaifen etc. take W-Gum as matrix, have synthesized Cross-linking Cationic Starch, to containing Cu
2+, Cd
2+deng water body have good removal effect (Wang Yuting, Cheng Ge. Carboxyl-containing Starch removes the research of toxic heavy metal ion in water body. Environmental Pollution and Control, 1996,18 (2): 16-18).Peng Changhong etc. have synthesized carboxyl grafting chitosan, and this product effectively can adsorb Pb
2+and Cb
2+deng (Han Huaifen, Chen little Juan, Jin Mantong. the synthesis of Cross-linking Cationic Starch and the absorption of heavy metal ion thereof. chemical industry environmental protection, 2005,25 (3): 325-237).Zhang Zhaomin etc. take Rhizoma amorphophalli glucomannan as raw material, vinyl cyanide is monomer, the optimised process being caused obtained grafting Rhizoma amorphophalli glucomannan by nitric acid berkelium ammonium is: initiator concentration 0.01mol/L, monomer concentration 1.6mol/L temperature of reaction 50 DEG C, reaction times 3h (Peng Changhong, Wang Yuting, Cheng Ke etc. the synthesis of carboxyl grafting chitosan and the absorption property of heavy metal ion thereof. environmental science, 1998,19 (2): 29-33).External also main at medicine to the research of KGM, 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; Mar1 ' 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 natural high moleculer eompound skeleton, makes the grafting polymer compound obtained have both some good characteristic of natural high moleculer eompound and synthetic macromolecular compound, the requirement of different application can be met.Given this, we intend is principal monomer with acrylamide, introduces carboxyl and KGM side base to increase the water-soluble of polymkeric substance, and introduce long-chain polyether, to improve the anti-shear performance of polymkeric substance in copolymer molecule chain.And KGM is natural polymer, and its chain is easily biodegradable, and can improve the biodegradability of polymkeric substance.
Summary of the invention
The object of the invention is to: in order to ensure carrying out smoothly of oil field oil production, spy provides a kind of acrylamide grafted copolymer oil-displacing agent and preparation method thereof.In order to reach this object, the present invention by the following technical solutions:
A kind of acrylamide grafted copolymer oil-displacing agent 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 Rhizoma amorphophalli glucomannan code name KGM tetra-kinds of structural units are formed; Its structure is as follows:
In (1) formula, n is the polymerization degree, for being greater than the integer of 0; The raw materials used proportioning of acrylamide grafted copolymer oil-displacing agent: in grams, monomer mass per-cent is quality, AM 51.5 ~ 58.8%, AA 40 ~ 45.5%, APEG 0.1 ~ 1.5%, KGM 0.1 ~ 1.5%; It is 5.3 × 10 that polymkeric substance glues equal relative molecular weight
6.
Prepare this acrylamide grafted copolymer oil-displacing agent, comprise following steps, reaction equation is as follows:
The first step: get quantitative KGM in 150mL there-necked flask, add appropriate water, stirs 30min at 30 DEG C of constant temperature, makes it fully swelling;
Second step: add quantitative AM, AA and APEG successively;
3rd step: regulate pH to designated value with 25%NaOH, system is made into the aqueous solution, logical nitrogen 10min;
4th step: constant temperature 30min at a set temperature, continues to pass into nitrogen 10-20min;
5th step: be warming up to temperature required rear constant temperature 20min, add initiator, more logical nitrogen 10min, at a constant temperature sealed reaction 12h, obtain pale yellow transparent viscosity liquid crude product;
6th step: crude product carried out roughing out and refine, drying and pulverize, obtain powder-like product AM/AA/APEG/KGM graft copolymer.
Final be made into monomer total mass percentage concentration is 10 ~ 25% aqueous solution.
The pH scope that in 3rd step and the 5th step, system is final is 6 ~ 9, and isothermal reaction temperature controls at 35 ~ 55 DEG C.
In 5th step, the one of water miscible hydrogen peroxide, ammonium persulphate, Potassium Persulphate, ceric ammonium nitrate chosen by initiator, or chooses the redox system of Potassium Persulphate and sodium bisulfite, ammonium persulphate and sodium bisulfite and ferrous ion and hydrogen peroxide composition; Initiator add-on is 0.1 ~ 1% of monomer total mass.
In 6th step, crude product carries out roughing out and refining method is: slowly to be poured into by pale yellow transparent viscosity liquid crude product in the beaker filling dehydrated alcohol and constantly to stir, obtaining white precipitate floss, and soak 5h; Unreacted Rhizoma amorphophalli glucomannan, graft copolymer and autopolymer are all insoluble in dehydrated alcohol, filtration under diminished pressure, under 50 DEG C of conditions, be dried to constant weight, obtain thick product; Be ethylene glycol-Glacial acetic acid mixed solvent immersion 10h of 2: 3 again by above-mentioned thick product volume ratio, then draw supernatant liquid repeatedly to soak with mixed solvent to remove autopolymer and unreacted Rhizoma amorphophalli glucomannan, finally obtain white solid precipitation with absolute ethanol washing, under 50 DEG C of conditions, be dried to constant weight, obtain purified product.
When 5th step adds initiator in joined solution, what add is the ceric ammonium nitrate solution that massfraction is respectively 20%.
Acrylamide grafted copolymer obtained by the present invention uses in tertiary oil production in oil field as oil-displacing agent.
The present invention has following beneficial effect: (1), in copolymer chain, introduces carboxylate groups and poly-hydroxy group, polymkeric substance is had good water-soluble; (2) by introducing Rhizoma amorphophalli glucomannan huge side base and allyl alcohol polyethenoxy ether chain, make the tackifying ability of polymkeric substance stronger, the multipolymer formed consumption in engineering obviously reduces, can be cost-saving.(3) introducing inside macromole due to large side base and the hydrophobic long-chain of Soxylat A 25-7, copolymer sheet reveals good heat-resistant salt-resistant and shear resistant.(4) grafting large side base is made a living object height molecular structure, is easier to degraded under long biological action, therefore less to underground environmental influence.
Accompanying drawing explanation
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
First get KGM in 150mL there-necked flask by the proportioning of table 1 Raw, add 20ml deionized water, stir 30min at 30 DEG C of constant temperature, make it fully swelling.Add AM successively again, AA and APEG, then regulate pH to designated value with 25%NaOH, system is made into the aqueous solution of 25%, logical nitrogen 10min, constant temperature 20min after being warming up to 40 DEG C, add initiator ceric ammonium nitrate, logical nitrogen 10min, after reacting 8h, obtains pale yellow transparent stickiness liquid at 40 DEG C again.Product is slowly poured in the beaker filling dehydrated alcohol and also constantly stir, obtain white precipitate floss, and soak 5h.Unreacted Rhizoma amorphophalli glucomannan, graft copolymer and autopolymer are all insoluble in dehydrated alcohol, filtration under diminished pressure, under 50 DEG C of conditions, be dried to constant weight, 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 repeatedly to soak with mixed solvent to remove autopolymer and unreacted Rhizoma amorphophalli glucomannan, finally obtain white solid precipitation with absolute ethanol washing, under 50 DEG C of conditions, be dried to constant weight and pulverize, obtaining powdery and refine graft copolymer product AM/AA/APEG/KGM.
Table 1 graft copolymer medicine dosage
Embodiment 2:AM/AA/APEG/KGM graft copolymer structure characterizes
By the infrared spectrum of graft copolymer AM/AA/APEG/KGM that goes out synthesized by embodiment 1 as shown in Figure 1.Multipolymer INFRARED SPECTRUM is shown at 3434cm in figure
-1place produces strong absorption peak, be the stretching vibration of the O-H in hydroxyl, and peak intensity is stronger, the existence of polyhydroxy structure is described; The stretching vibration of N-H is at 3300cm
-1left and right, because hydroxyl group absorption peak is very strong, N-H is absorbed vibration peak and covered, therefore N-H absorption peak does not show; At 2938cm
-1it is-CH that place produces strong absorption peak
2-stretching vibration, at 1677cm
-1be the stretching vibration of-C=O, prove to there is amide structure in polymer molecule, product is 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 ", with tetrapolymer prepared by embodiment 2, be mixed with the solution of 0.1wt%, at 30 ± 0.1 DEG C, the intrinsic viscosity using progressively dilution method to record graft copolymer is 1129.3mL/g.Utilize experimental formula M=802 [η]
1.25, M is bonded restorations, and [η] is intrinsic viscosity, 802, and 1.25 are empirical constant.Can be calculated polymkeric substance to glue equal relative molecular weight 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 gone out synthesized by embodiment 1 is made into the aqueous solution of 0.02 ~ 0.1%, at 30 DEG C with Brookfield LVTDV-III viscometer at shearing rate 7.34s
-1measure the apparent viscosity of solution under condition, 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 introduce poly-hydroxy side base within connecting at macromole, under suitable concentration, the effect of power between multiple hydroxyl, causes viscosity to have larger increasing.In a word, the Efficient Adhesive Promotion of AM/AA/APEG/KGM graft copolymer is obvious, is suitable for making oil-displacing agent.
The embodiment 5:AM/AA/APEG/KGM graft copolymer property sheared is investigated
Graft copolymer prepared by embodiment 1 is mixed with the 0.1wt% aqueous solution, is 30 DEG C in temperature, with HAAKERheoStress6000 rheometer in shearing rate from 170s
-1rise to 510s
-1, then from 510s
-1drop to 170s
-1under condition, measure the viscosity B coefficent of polymers soln, data are as Fig. 3.Can find from Fig. 3: at constant shear rate 170s
-1lower for some time, apparent viscosity of polymer is tending towards constant; When raising shearing rate to 510s suddenly
-1time, apparent viscosity is reduced to 313mPa.s, and this meets the character of superpolymer fluid, when shearing rate gets back to 170s again
-1time, apparent viscosity is almost surely held in again the apparent viscosity 363mPa.s under the shearing rate of beginning, and result fully shows, this graft copolymer has obvious viscosity save power under 30 DEG C of high shear rate conditions, and anti-shear performance is better.
Embodiment 6:AM/AA/APEG/KGM graft copolymer temperature tolerance is investigated
Graft copolymer obtained in embodiment 1 is mixed with 0.1% aqueous solution, and with HAAKERheoStress6000 rheometer at temperature is 33 ~ 116 DEG C, measure the viscosity B coefficent situation of polymers soln, data are 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 is elevated to 60 DEG C time, viscosity retention ratio can reach 91.3%, and when temperature rises to 90 DEG C again time, viscosity retention ratio is 74.2%, but when temperature is elevated to 100 DEG C, apparent viscosity sharply declines, and viscosity retention ratio is about 63.6%.Result shows, this graft copolymer has good viscosity save power below 100 DEG C.
Indoor raising recovery ratio (EOR) experiment of embodiment 7:AM/AA/APEG/KGM graft copolymer
Multipolymer prepared by embodiment 1 being mixed with concentration is the 500mg/L aqueous solution, and shearing rate is 7.34s
-1time, apparent viscosity is 158.4mPa.s, total mineralization 7000mg/L (MgCl
21000mg/L, NaCl5000, CaCl
21000mg/L), simulating oil deposit temperature 65 DEG C; Simulated oil viscosity: 74.6mPas (65 DEG C, shearing rate 7.34S
-1), one dimension sand-packed model: Φ 25x500, water displacing oil: mixed water injection water is with 1mL/min injection speed displacement simulation oil, and inject injection rate for 0.3PV, 500mg/L polymers soln with 1mL/min, follow-up water 1ml/min, water saturation reaches 98.5%.With do displacement of reservoir oil laboratory experiment with clear water under same condition and compare, this polymkeric substance improves Simulation of Crude Oil recovery ratio can reach 11.3%.
Claims (8)
1. an acrylamide grafted copolymer oil-displacing agent, it is characterized in that: this acrylamide grafted copolymer oil-displacing agent is by acrylamide code name AM, vinylformic acid code name AA, allyl alcohol polyethenoxy ether code name APEG, and Rhizoma amorphophalli glucomannan code name KGM tetra-kinds of structural units are formed;
Its structure is as follows:
In (1) formula, n is the polymerization degree, for being greater than the integer of 0; The raw materials used proportioning of acrylamide grafted copolymer oil-displacing agent: in grams, monomer mass per-cent is quality, AM 51.5 ~ 58.8%, AA 40 ~ 45.5%, APEG 0.1 ~ 1.5%, KGM 0.1 ~ 1.5%; It is 5.3 × 10 that polymkeric substance glues equal relative molecular weight
6.
2. an acrylamide grafted copolymer oil-displacing agent according to claim 1, is characterized in that:
Prepare this acrylamide grafted copolymer oil-displacing agent, comprise following steps, reaction equation is as follows:
The first step: get quantitative KGM in 150mL there-necked flask, add appropriate water, stirs 30min at 30 DEG C of constant temperature, makes it fully swelling;
Second step: add quantitative AM successively, AA and APEG;
3rd step: regulate pH to designated value with 25%NaOH, system is made into the aqueous solution, logical nitrogen 10min;
4th step: constant temperature 30min at a set temperature, continues to pass into nitrogen 10-20min;
5th step: be warming up to temperature required rear constant temperature 20min, add initiator, more logical nitrogen 10min, at a constant temperature sealed reaction 8h, obtain pale yellow transparent stickiness liquid crude product;
6th step: crude product carried out roughing out and refine, drying and pulverize, obtain powder-like product AM/AA/APEG/KGM graft copolymer.
3. an acrylamide grafted copolymer oil-displacing agent according to claim 2, is characterized in that: the final monomer total mass percentage concentration that is made into is 10 ~ 25% aqueous solution.
4. an acrylamide grafted copolymer oil-displacing agent according to claim 2, is characterized in that: the pH scope of end reaction system is 6 ~ 9, and temperature of reaction controls at 35 ~ 55 DEG C.
5. an acrylamide grafted copolymer oil-displacing agent according to claim 2, is characterized in that:
The one of water miscible hydrogen peroxide, ammonium persulphate, Potassium Persulphate, ceric ammonium nitrate chosen by initiator, or chooses the redox system of Potassium Persulphate-sodium bisulfite, ammonium persulphate and sodium bisulfite and ferrous ion and hydrogen peroxide composition; Initiator add-on is 0.1 ~ 1% of monomer total mass.
6. an acrylamide grafted copolymer oil-displacing agent according to claim 2, is characterized in that:
Crude product carries out roughing out and refining method is: slowly poured into by pale yellow transparent viscosity liquid crude product in the beaker filling dehydrated alcohol and also constantly stir, obtain white precipitate floss, and soak 5h; Unreacted Rhizoma amorphophalli glucomannan, graft copolymer and autopolymer are all insoluble in dehydrated alcohol, filtration under diminished pressure, under 50 DEG C of conditions, be dried to constant weight, obtain thick product; Be ethylene glycol-Glacial acetic acid mixed solvent immersion 10h of 2: 3 again by above-mentioned thick product volume ratio, then draw supernatant liquid repeatedly to soak with mixed solvent to remove autopolymer and unreacted Rhizoma amorphophalli glucomannan, finally obtain white solid precipitation with absolute ethanol washing, under 50 DEG C of conditions, be dried to constant weight, obtain purified product.
7. an acrylamide grafted copolymer oil-displacing agent according to claim 2, is characterized in that:
When adding initiator in joined solution, what add is the ceric ammonium nitrate solution that massfraction is respectively 20%.
8. the acrylamide grafted copolymer obtained by claim 2 uses in tertiary oil production in oil field as oil-displacing agent.
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