CN103205247B - Swollen granular profile control agent and its preparation method and application is delayed in modification - Google Patents
Swollen granular profile control agent and its preparation method and application is delayed in modification Download PDFInfo
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Abstract
The present invention relates to a kind of for oil field deep profile control transfer drive, oilwell water shutoff there is granular profile control agent of slow expansion character and preparation method thereof and the application in field of petroleum exploitation.It comprises the component of following weight part: water-soluble monomer 4-20 part, oil-soluble monomer 10-50 part, water-soluble cross-linker 0.01-1 part, oil-soluble crosslinking agent 0.02-2 part, tensio-active agent 1-10 part, water soluble starter 0.05-0.5 part, oil-soluble initiator 0.001-0.25 part, coupling agent 0.05-0.5 part, alkali 0-5 part, deionized water 30-70 part.Swollen granular profile control agent is delayed in modification of the present invention, overcome existing expanded polystyrene veneer particulate water absorbent speed of expansion fast, expand after particle really up to the mark, the defect of oil field deep profile control can not be used for.Can be used for oilwell water shutoff, high water cut oil field deep rock tunneling, improving ecology, polymer flooding, the Flooding Efficiency of surfactant flooding, improve oil recovery.
Description
Technical field
The present invention relates to a kind of profile-controlling and plugging agent, particularly relate to a kind of for oil field deep profile control transfer drive, oilwell water shutoff there is granular profile control agent of slow expansion character and preparation method thereof and the application in field of petroleum exploitation.
Background technology
Due to the nonuniformity on stratum, so oil-displacing agent (as water) flow profile is in the earth formation uneven.Improve the sweep efficiency of oil-displacing agent thus improve recovery ratio, its flow profile and profile control will be adjusted, then needing during profile control to use amendment (amendment, Zhao Fulin, " University of Petroleum's journal (natural science edition) " April nineteen ninety).
Along with the development of oil cause, increasing novel profile control adjusting driving agnet obtains application on oil field.Water flooding enters the middle and later periods, due to the impact of formation heterogeneity, causes and injects water and advance by leaps and bounds along most permeable zone, cause well water rise fast, water logging early, the degree of injecting ripples and low permeability layer is low, water flooding effectiveness is poor.Although common expanded polystyrene veneer particle has played very large effect in deep profile controlling, also good effect is achieved, but its water-swellable excessive velocities, cause amendment in the earth formation can not to oil reservoir deep migration, be blocked in immediate vicinity of wellbore, can not reach the object of deep profile controlling transfer drive, its intensity also declines fast along with speed of expansion, product is caused to block up in the earth formation incessantly, block up loosely, poor stability.To such an extent as to limit it and apply in high water cut oil field deep profile controlling transfer drive.Patent ZL200910010818.1 discloses a kind of expanding flow-gel profile-controlling and plugging agent, is mixed by polyacrylamide solution with boron modified phenolic resin delayed crosslinker, controls temperature of reaction 40-100 DEG C, pH value 7.2-8.0 polyreaction and obtains.This profile-controlling and plugging agent at water swellability, delay bridging property, salt-resistant temperature obtains obvious improvement, but the plugging agent of this research belongs to gel-like, product need be injected into Gelling down hole during use, controllability and operability far away from granular profile control agent, so be badly in need of developing a kind of have slow to expand, pliable and tough deformability and granular profile control agent easy to use.
Summary of the invention
For the problems referred to above, the technical problem to be solved in the present invention be to provide a kind of have slow to expand, pliable and tough deformation performance and granular profile control agent easy to use.
For reaching above-mentioned purpose, the invention provides a kind of modification and delay swollen granular profile control agent, comprise the component of following weight part: water-soluble monomer 4-20 part, oil-soluble monomer 10-50 part, water-soluble cross-linker 0.01-1 part, oil-soluble crosslinking agent 0.02-2 part, tensio-active agent 1-10 part, water soluble starter 0.05-0.5 part, oil-soluble initiator 0.001-0.25 part, coupling agent 0.05-0.5 part, alkali 0-5 part, deionized water 30-70 part; Preferably, the weight part of described each component is: water-soluble monomer 8-15 part, oil-soluble monomer 20-40 part, water-soluble cross-linker 0.1-0.5 part, oil-soluble crosslinking agent 0.1-1 part, tensio-active agent 2-8 part, water soluble starter 0.1-0.3 part, oil-soluble initiator 0.005-0.2 part, coupling agent 0.1-0.3 part, alkali 0-2 part, deionized water 45-65 part.
Further, swollen granular profile control agent is delayed in modification of the present invention, wherein preferred described water-soluble monomer is selected from acrylamide, vinylformic acid, hy-droxybutyl, sodium acrylate, Methacrylamide, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (Methacryloxyethyltrimethyl ammonium chloride, DMC), N, N-DMAA, vinyl pyrrolidone, N hydroxymethyl acrylamide, acryloyl morpholine, 2-acrylamide-2-methyl propane sulfonic (2-Acrylamide-2-methylpro panesulfonic acid, AMPS) one or more and in vinylformic acid glycol ester compound are with the mixture of arbitrary proportion.
Swollen granular profile control agent is delayed in modification of the present invention, wherein preferred described oil-soluble monomer be selected from one or more in methyl acrylate, ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, butyl methacrylate, ethyl acrylate, β-dimethyl-aminoethylmethacrylate, vinylbenzene, Propenoic acid, 2-methyl, isobutyl ester and glytidyl methacrylate with the mixture of arbitrary proportion.
Swollen granular profile control agent is delayed in modification of the present invention, and wherein preferred described water-soluble cross-linker is selected from one or more in methene base bisacrylamide, diallyldimethylammonium chloride and polyethyleneglycol diacrylate with the mixture of arbitrary proportion.
Swollen granular profile control agent is delayed in modification of the present invention, wherein preferred described oil-soluble crosslinking agent be selected from one or more in diallyl diethyl malonate, Vinylstyrene, Phthalic acid, diallyl ester, diallyl isophthalate and DATBP with the mixture of arbitrary proportion.
Swollen granular profile control agent is delayed in modification of the present invention, wherein preferred described water soluble starter be selected from ammonium persulphate, Potassium Persulphate, Sodium Persulfate, S-WAT and sodium bisulfite one or more with the mixture of arbitrary proportion;
Preferred described oil-soluble initiator is Diisopropyl azodicarboxylate or benzoyl peroxide;
Preferred described coupling agent is silane coupling agent or titanate coupling agent;
Preferred described tensio-active agent is selected from one or more in sapn (sorbitan fatty acid ester), tween, sodium laurylsulfonate and alkylphenol polyoxyethylene with the mixture of arbitrary proportion;
Preferred described alkali is sodium carbonate, sodium bicarbonate or sodium hydroxide.
More preferably described sapn is selected from Arlacel-20, Arlacel-40, Arlacel-60 or Arlacel-80; Described tween be selected from one or more in tween 20, Tween-40, Tween-60 and tween-80 with the mixture of arbitrary proportion; Described silane coupling agent be selected from one or more in KH550, KH560, KH570, KH792, DL602 and DL171 with the mixture of arbitrary proportion.
Swollen granular profile control agent is delayed in modification of the present invention, and above-mentioned each feed composition is commercially available prod.
The invention still further relates to the method that swollen granular profile control agent is delayed in the above-mentioned modification of preparation, it comprises the following steps:
(1) aqueous phase solution preparation: water-soluble monomer, water-soluble cross-linker are dissolved in deionized water, adds alkali and tensio-active agent again after stirring, be stirred to transparent sediment-free;
(2) oil-based system preparation: oil-soluble crosslinking agent is joined in oil-soluble monomer, be stirred to and dissolve completely, then add oil-soluble initiator and coupling agent, continue to be stirred to and dissolve completely, finally add tensio-active agent, be stirred to and disperse completely;
(3) emulsion system preparation: the aqueous phase solution that step (1) obtains progressively is joined in the oil-based system that step (2) obtains, fully stir or use high-speed emulsifying machine emulsification, obtaining polymerized emulsion system;
(4) polyreaction: pass into nitrogen in above-mentioned emulsion system, to displace oxygen wherein, water soluble starter is added in emulsion system, stir, put into 10-45 DEG C of environment and react 0.5h-4h, after system temperature is raised to 80-90 DEG C, then put into the 70-90 DEG C of aging 3-4h of environment, namely polyreaction completes, then granulation and get final product.
Above-mentionedly prepare modification and delay in the method for swollen granular profile control agent, step (1) aqueous phase solution can also be prepared by the following method: dissolve in deionized water by water-soluble monomer, water-soluble cross-linker and alkali, add tensio-active agent again after stirring, be stirred to transparent sediment-free.
The application of swollen granular profile control agent is delayed in the above-mentioned modification of the present invention, uses it for field of petroleum exploitation, further, can be used for oil field deep profile control transfer drive, oilwell water shutoff.
The invention difference from existing technology is, modification of the present invention is delayed swollen granular profile control agent and is contained each feed composition of approrpiate wts proportioning, overcome existing common expanded polystyrene veneer particulate water absorbent speed of expansion fast, expand after particle really up to the mark, the defect of oil field deep profile control transfer drive can not be used for.Modification of the present invention delays swollen granular profile control agent owing to utilizing the interpenetrating(polymer)networks of oil soluble macromole and water-soluble macromolecule composition, and this network progressively makes system water-retaining capacity reach capacity by capillary suction principle, so have slow expansion characteristics; Owing to introducing flexible unit in system, can flexible nature be shown after polymerisation, there is good deformability; Suitable oil-soluble ingredient and the collocation of water soluble ingredient enhance the stability of system, deep profile controlling transfer drive, oilwell water shutoff can be used in, can high salt tolerance high temperature resistance, can be used for high temperature and high salt oil and water well, high water cut oil field deep rock tunneling, improving ecology, polymer flooding, the Flooding Efficiency of surfactant flooding, improves oil recovery.
Accompanying drawing explanation
Fig. 1 is the present invention and common aspect swollen grain expansion multiple mensuration figure;
Fig. 2 is the present invention and common volume expansion grain elastic modulus detection figure.
Embodiment
Below in conjunction with embodiment and testing data, to above-mentioned being described in more detail with other technical characteristic and advantage of the present invention.
Embodiment 1
(1) aqueous phase solution preparation: 4kg acrylamide, 0.01kg methene base acrylamide and 0.03kg sodium hydroxide are dissolved in 30kg deionized water, adds 1kg tween-80 again after stirring, be stirred to transparent sediment-free;
(2) oil-based system preparation: 0.02kg diallyl diethyl malonate is joined in 10kg methyl acrylate, be stirred to and dissolve completely, add 0.001kg Diisopropyl azodicarboxylate (AIBN) and 0.05kg Silane coupling agent KH550 again, continue to be stirred to and dissolve completely, finally add 1kg Arlacel-40, be stirred to and disperse completely;
(3) emulsion system preparation: the aqueous phase solution that step (1) obtains progressively is joined in the oil-based system that step (2) obtains, fully stir 2h, obtain polymerized emulsion system;
(4) polyreaction: pass into nitrogen in above-mentioned emulsion system, to displace oxygen wherein, the S-WAT of 0.05kg ammonium persulphate and 0.05kg is added in emulsion system, stir, put into 40 DEG C of environment and react 1h, when temperature is elevated to 80 DEG C after system solidification, then put into 80 DEG C of aging 3h of environment, namely polyreaction completes, then granulation and get final product.
Embodiment 2
(1) aqueous phase solution preparation: 20kg hy-droxybutyl, 1kg diallyldimethylammonium chloride are dissolved in 70kg deionized water, adds 3kg Tween-60 again after stirring, be stirred to transparent sediment-free;
(2) oil-based system preparation: 2kg Phthalic acid, diallyl ester is joined in 50kg methyl methacrylate, be stirred to and dissolve completely, add 0.25kg benzoyl peroxide and 0.5kg silane coupling agent KH792 again, continue to be stirred to and dissolve completely, finally add 3kg Arlacel-40, be stirred to and disperse completely;
(3) emulsion system preparation: the aqueous phase solution that step (1) obtains progressively is joined in the oil-based system that step (2) obtains, fully stir 3h, obtain polymerized emulsion system;
(4) polyreaction: pass into nitrogen in above-mentioned emulsion system, to displace oxygen wherein, the S-WAT of 0.5kg Potassium Persulphate and 0.28kg is added in emulsion system, stir, put into 45 DEG C of environment and react 40min, after system solidification, temperature rises to 80 DEG C, then puts into 80 DEG C of aging 3.5h of environment, namely polyreaction completes, then granulation and get final product.
Embodiment 3
(1) aqueous phase solution preparation: 10kg MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, 0.1kg polyethyleneglycol diacrylate are dissolved in 40kg deionized water, adds 1kg tween 20 again after stirring, be stirred to transparent sediment-free;
(2) oil-based system preparation: 0.1kg diallyl isophthalate is joined in 20kg ethyl acrylate, be stirred to and dissolve completely, add 0.005kg benzoyl peroxide and 0.1kg titanate coupling agent again, continue to be stirred to and dissolve completely, finally add 1kg sodium laurylsulfonate, be stirred to and disperse completely;
(3) emulsion system preparation: the aqueous phase solution that step (1) obtains progressively is joined in the oil-based system that step (2) obtains, fully stir 2.5h, obtain polymerized emulsion system;
(4) polyreaction: pass into nitrogen in above-mentioned emulsion system, to displace oxygen wherein, 0.25kg Sodium Persulfate and 0.1kg sodium bisulfite are added in emulsion system, stir, put into 25 DEG C of environment and react 3h, after system solidification, temperature rises to 85 DEG C, then puts into 85 DEG C of aging 4h of environment, namely polyreaction completes, then granulation and get final product.
Embodiment 4
(1) aqueous phase solution preparation: 18kg2-acrylamide-2-methyl propane sulfonic, 0.5kg methene base bisacrylamide are dissolved in 60kg deionized water, adds 4kg Tween-40 again after stirring, be stirred to transparent sediment-free;
(2) oil-based system preparation: 1kg DATBP is joined in 40kg glytidyl methacrylate, be stirred to and dissolve completely, add 0.1kg Diisopropyl azodicarboxylate (AIBN) and 0.3kg titanate coupling agent again, continue to be stirred to and dissolve completely, finally add 4kg alkylphenol polyoxyethylene, be stirred to and disperse completely;
(3) emulsion system preparation: the aqueous phase solution that step (1) obtains progressively is joined in the oil-based system that step (2) obtains, fully stir 2h, obtain polymerized emulsion system;
(4) polyreaction: pass into nitrogen in above-mentioned emulsion system, to displace oxygen wherein, 0.5kg ammonium persulphate and 0.3kg S-WAT are added in emulsion system, stir, put into 45 DEG C of environment and react 40min, after system solidification, temperature rises to 80 DEG C, then puts into 90 DEG C of aging 4h of environment, namely polyreaction completes, then granulation and get final product.
The mensuration of swollen granular profile control agent and the swollen grain expansion multiple of common aspect is delayed in test example 1 modification
1 instrument
Plastic Bottle, graduated cylinder: 250mL, thermostat container, precision electronic balance, sensibility reciprocal 0.01g, spoon, standard sieve, watch-glass, vacuum pump using circulatory water, Büchner funnel, filter paper, filter flask, analytical balance: precision 0.1mg, specific gravity flask: 25cm
3, water bath with thermostatic control: 23 ± 0.5 DEG C, thermometer: precision 0.5 DEG C, beaker etc.
2 determination steps
2.1 measure by the method specified in standard GB/T 4472-1984 the density that modification of the present invention delays swollen granular profile control agent and the swollen particle sample of common aspect, are considered as ρ.
2.1.1 operation steps
2.1.1.1 claim the quality of empty specific gravity flask, then add sample mass, then injection part measures distilled water, slight oscillatory, after sample is fully wetting, continues specific gravity flask to fill, must not have bubble in specimen surface and distilled water.
2.1.1.2 by filling the specific gravity flask of distilled water and sample, cover tightly bottle cap, put into (23 ± 0.5 DEG C) water-bath, more than constant temperature 30min, taking-up is dried, and weighs immediately.
2.1.1.3 specific gravity flask is cleaned, dry, be full of distilled water, after putting into water bath with thermostatic control, repeat aforesaid operations.
2.1.2 test-results
2.1.2.1 the volume V(cm of specific gravity flask
3) calculate by formula (1):
In formula:
The quality of m-empty specific gravity flask, g;
M
1-be full of the quality of specific gravity flask measuring medium, g;
ρ
0the density of medium is measured, g/cm at-mensuration temperature
3.
2.1.2.2 the volume V of distilled water in specific gravity flask
1(cm
3) calculate by formula (2):
In formula:
M
2-put into appropriate sample and be full of the specific gravity flask quality of distilled water, g;
M
3-put into the specific gravity flask quality of appropriate sample, g.
2.1.2.3 the density p (g/cm of sample
3) calculate by formula (3):
2.1.2.4 modification of the present invention delays the density of swollen granular profile control agent and the swollen particle sample of common aspect in table 1 and table 2:
Swollen granular profile control agent density measurement result is delayed in table 1 modification
The swollen pellet density test result of table 2 common aspect
2.2 saline: accurately prepare the sodium chloride aqueous solution 3L of 0.095% with distilled water.
2.3 get about 150g sample to be tested, filter flask and vacuum pump are connected, double-layer filter paper is laid in Büchner funnel, dark and damp with a small amount of water, then sample to be tested is laid in funnel, open vacuum pump switch, be evacuated to that its lower portion is anhydrous to drip, with filter paper, sample to be tested surface-moisture is dried again, utilize the mode of this suction filtration by particle surface with taking the sample after 5.00g process after moisture removal in precision electronic balance, be considered as m
0.
Sample after weighing is put into Plastic Bottle by 2.4.
2.5 measure 240mL salt solution with 250mL graduated cylinder, are considered as H
0, add and be equipped with in the Plastic Bottle of sample, cover plastic bottle cap, put into thermostat container, calorstat temperature is set as 45 ± 1 DEG C.This test need make a series of plastic sample bottles that equivalent sample, equal-volume salt solution are housed, concrete reference is table 3,4 below, modification of the present invention is delayed the test of swollen granular profile control agent and is got 21 time points altogether, each time point needs 3 parallel tests, so at least need 63 plastic sample bottles that equivalent granular profile control agent of the present invention and salt solution are housed; And with regard to the common volume expansion grain of control sample, then need minimum 15 plastic sample bottles.
2.6 according to the time point shown in table 3 and table 4, and each taking-up 3 same plastic sample bottles, are cooled to room temperature, gets standard sieve and filters the sample after immersion in Plastic Bottle, measure in Plastic Bottle the volume remaining water, be considered as H with 250mL graduated cylinder
1.
2.7 as mentioned above, and this test is parallel carries out three times, averages after three parallel sample measured value summations.When the single measured value of sample and mean deviation are greater than 0.1, then need mensuration of resampling.
The calculating of 3 expansion multiples:
In formula:
The volumetric expansion multiple of C-sample, doubly;
M
0the quality of-sample, g;
The density of ρ-sample, g/cm
3;
H
0the volume of salt solution is initially added, mL in-Plastic Bottle;
H
1the volume of the rear residual brine of sample expansion in-Plastic Bottle, mL.
4 modifications delay swollen granular profile control agent and common aspect swollen grain expansion multiple measurement result in table 3, table 4 and Fig. 1.
Swollen granular profile control agent expansion multiple is delayed in table 3 modification
The swollen grain expansion multiple of table 4 common aspect
From table 3, table 4, common volume expansion grain volumetric expansion multiple the 0.4th day time reaches 15.0, and it is then slow expansion that swollen granular profile control agent is delayed in modification of the present invention, and the 50th day time, volumetric expansion multiple is only 9.30.Therefore the present invention is slow compared with the swollen grain expansion of common aspect.
The mensuration of swollen granular profile control agent and common volume expansion grain Young's modulus is delayed in test example 2 modification
1 instrument
Elastic modulus tester, general purpose oscialloscope, vernier callipers, sample.
2 test procedures
The method of 2.1 measurement Young's modulus:
Under certain condition (L > d), the natural frequency of sample vibration depends on that its factor such as geometrical shape, size, quality is relevant, Young's modulus:
In formula:
E-Young's modulus, KPa;
The length of L-sample, m;
The quality of m-sample, g;
F-sample fundamental resonance frequency, Hz;
If the natural frequency of (as room temperature) sample under measuring certain temperature in experiment, size, quality know its geometrical shape, just can calculate the Young's modulus of sample when this temperature.In formula, J represents the inertia distance of test rod, and main relevant with the geometrical shape of sample, inertia apart from formula is:
J=∫
sy
2ds （5）
In formula:
The cross-sectional area of S-sample, m
2;
The cross-sectional diameter of d-sample, m;
The lateral vibration displacement of y-sample, m.
The Young's modulus of circular specimen is obtained by formula (4) and (5):
The making of 2.2 samples
It is 5-10cm that sample modification of the present invention being delayed swollen granular profile control agent and common volume expansion grain is all made into length, and diameter of section is the sample of 2cm, and swollen granular profile control agent is delayed in modification of the present invention and common volume expansion grain respectively makes 8 samples.
2.3 install sample
Carefully hung on two suspensions by sample, require that suspension is axially vertical with sample, sample keeps transverse horizontal, and two suspension hanging points are identical to the end-point distances of sample, and remain static.
2.4 online
Connect oscilloscope, adjustment oscilloscope is in running order.
2.5 measure
First calculate two node locations doing fundamental frequency lateral vibration of sample and mark on sample, then three right suspension points are each side got at node, two suspensions are hung on outermost suspension point, conditioning signal projector knob, find the resonant frequency of sample and then successively two suspension wires moved to the inside simultaneously, each resonant frequency surveying three pairs of suspension point places about node, and record.
The calculating of the Young's modulus of 3 samples:
In formula:
E-Young's modulus, KPa;
The length of L-sample, m;
The cross-sectional diameter of d-sample, m;
M
0the quality of-sample, g;
F-sample fundamental resonance frequency, Hz.
4 modifications delay that swollen granular profile control agent and common volume expansion grain elastic modulus detection the results are shown in Table 5, table 6 and Fig. 2.
Swollen granular profile control agent elastic modulus detection result is delayed in table 5 modification
| Sequence number L (m) | m 0(g) | d(m) | Average f (Hz) | E(KPa) |
| 10.100 | 32.97 | 0.02 | 6.70 | 14.86 |
| 20.095 | 31.32 | 0.02 | 7.43 | 14.88 |
| 30.090 | 29.67 | 0.02 | 8.27 | 14.88 |
| 40.085 | 28.02 | 0.02 | 9.28 | 14.90 |
| 50.080 | 26.38 | 0.02 | 10.47 | 15.00 |
| 60.075 | 24.73 | 0.02 | 11.96 | 15.00 |
| 70.070 | 23.08 | 0.02 | 13.68 | 15.02 |
| 80.065 | 21.43 | 0.02 | 15.95 | 15.04 |
Table 6 common volume expansion grain elastic modulus detection result
| Sequence number L (m) | m 0(g) | d(m) | Average f (Hz) | E(KPa) |
| 10.100 | 47.10 | 0.02 | 3.10 | 4.55 |
| 20.095 | 44.75 | 0.02 | 3.44 | 4.56 |
| 30.090 | 42.39 | 0.02 | 3.84 | 4.6 |
| 40.085 | 40.04 | 0.02 | 4.34 | 4.65 |
| 50.080 | 37.68 | 0.02 | 4.92 | 4.7 |
| 60.075 | 35.33 | 0.02 | 5.60 | 4.7 |
| 70.070 | 32.97 | 0.02 | 6.45 | 4.72 |
| 80.065 | 30.62 | 0.02 | 7.49 | 4.74 |
Swollen granular profile control agent Young's modulus is delayed apparently higher than common volume expansion grain by table 5, the known modification of the present invention of table 6.
Above-described embodiment is only be described the preferred embodiment of the present invention; not scope of the present invention is limited; under not departing from the present invention and designing the prerequisite of spirit; the various distortion that those of ordinary skill in the art make technical scheme of the present invention and improvement, all should fall in protection domain that claims of the present invention determines.
Claims (8)
1. swollen granular profile control agent is delayed in a modification, it is characterized in that, comprise the component of following weight part: water-soluble monomer 4-20 part, oil-soluble monomer 10-50 part, water-soluble cross-linker 0.01-1 part, oil-soluble crosslinking agent 0.02-2 part, tensio-active agent 1-10 part, water soluble starter 0.05-0.5 part, oil-soluble initiator 0.001-0.25 part, coupling agent 0.05-0.5 part, alkali 0-5 part, deionized water 30-70 part;
Wherein, described water-soluble monomer is selected from one or more in acrylamide, vinylformic acid, hy-droxybutyl, sodium acrylate, Methacrylamide, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, N,N-DMAA, vinyl pyrrolidone, N hydroxymethyl acrylamide, acryloyl morpholine, 2-acrylamide-2-methyl propane sulfonic and vinylformic acid glycol ester with the mixture of arbitrary proportion;
Described oil-soluble monomer be selected from one or more in methyl acrylate, ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, butyl methacrylate, ethyl acrylate, β-dimethyl-aminoethylmethacrylate, vinylbenzene, Propenoic acid, 2-methyl, isobutyl ester and glytidyl methacrylate with the mixture of arbitrary proportion;
Described water-soluble cross-linker is selected from one or more in methene base bisacrylamide, diallyldimethylammonium chloride and polyethyleneglycol diacrylate with the mixture of arbitrary proportion;
Described oil-soluble crosslinking agent be selected from one or more in diallyl diethyl malonate, Vinylstyrene, Phthalic acid, diallyl ester, diallyl isophthalate and DATBP with the mixture of arbitrary proportion;
Described water soluble starter be selected from ammonium persulphate, Potassium Persulphate, Sodium Persulfate, S-WAT and sodium bisulfite one or more with the mixture of arbitrary proportion;
Described oil-soluble initiator is Diisopropyl azodicarboxylate or benzoyl peroxide;
Described coupling agent is silane coupling agent or titanate coupling agent;
Prepare the method that swollen granular profile control agent is delayed in described modification, comprise the following steps:
(1) aqueous phase solution preparation: water-soluble monomer, water-soluble cross-linker are dissolved in deionized water, adds alkali and tensio-active agent again after stirring, be stirred to transparent sediment-free;
(2) oil-based system preparation: oil-soluble crosslinking agent is joined in oil-soluble monomer, be stirred to and dissolve completely, then add oil-soluble initiator and coupling agent, continue to be stirred to and dissolve completely, finally add tensio-active agent, be stirred to and disperse completely;
(3) emulsion system preparation: the aqueous phase solution that step (1) obtains progressively is joined in the oil-based system that step (2) obtains, fully stir or use high-speed emulsifying machine emulsification, obtaining polymerized emulsion system;
(4) polyreaction: pass into nitrogen in above-mentioned emulsion system, to displace oxygen wherein, water soluble starter is added in emulsion system, stir, put into 10-45 DEG C of environment and react 0.5h-4h, after system temperature is raised to 80-90 DEG C, then put into the 70-90 DEG C of aging 3-4h of environment, namely polyreaction completes, then granulation and get final product.
2. swollen granular profile control agent is delayed in modification according to claim 1, it is characterized in that: the weight part of described each component is: water-soluble monomer 8-15 part, oil-soluble monomer 20-40 part, water-soluble cross-linker 0.1-0.5 part, oil-soluble crosslinking agent 0.1-1 part, tensio-active agent 2-8 part, water soluble starter 0.1-0.3 part, oil-soluble initiator 0.005-0.2 part, coupling agent 0.1-0.3 part, alkali 0-2 part, deionized water 45-65 part.
3. swollen granular profile control agent is delayed in modification according to claim 1 and 2, it is characterized in that: described tensio-active agent be selected from one or more in sapn, tween, sodium laurylsulfonate and alkylphenol polyoxyethylene with the mixture of arbitrary proportion;
Described alkali is sodium carbonate, sodium bicarbonate or sodium hydroxide.
4. swollen granular profile control agent is delayed in modification according to claim 3, it is characterized in that: described sapn is selected from Arlacel-20, Arlacel-40, Arlacel-60 or Arlacel-80;
Described tween be selected from one or more in tween 20, Tween-40, Tween-60 and tween-80 with the mixture of arbitrary proportion.
5. swollen granular profile control agent is delayed in modification according to claim 1, it is characterized in that: described silane coupling agent be selected from one or more in KH550, KH560, KH570, KH792, DL602 and DL171 with the mixture of arbitrary proportion.
6. swollen granular profile control agent is delayed in modification according to claim 1, it is characterized in that, step (1) aqueous phase solution is prepared: dissolve in deionized water by water-soluble monomer, water-soluble cross-linker and alkali, add tensio-active agent again after stirring, be stirred to transparent sediment-free.
7. the application of swollen granular profile control agent is delayed in the modification described in any one of claim 1-6, it is characterized in that: use it for field of petroleum exploitation.
8. the application of swollen granular profile control agent is delayed in modification according to claim 7, it is characterized in that: use it for oil field deep profile control transfer drive, oilwell water shutoff.
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| CN201310108385.9A CN103205247B (en) | 2013-03-29 | 2013-03-29 | Swollen granular profile control agent and its preparation method and application is delayed in modification |
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| CN101619119A (en) * | 2009-05-26 | 2010-01-06 | 中国石油大学(华东) | Polymer microspheres for high temperature hypersalinity reservoir deep profile control and preparation method thereof |
| CN102382244B (en) * | 2011-08-17 | 2013-02-06 | 西南石油大学 | Gelation-delayed in-situ polymerized water shutoff gel for high-temperature reservoirs |
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