CN101724384B - Preparation method of high strength elastic slow-expansion water-absorption particle diverting agent - Google Patents

Abstract

The invention relates to a preparation method of a high strength elastic slow-expansion water-absorption particle diverting agent, comprising the following steps of: according to the total mass of 100 percent, weighing 10-20 percent of monomer, 0.5-1percent of initiator, 0.01-0.1percent of crosslinker, 30-50 percent of natural rubber or/and 0.1-1.0 of speed control agent and the balance of water, generating the cross-linking polymerization reaction at the temperature of 40-80 DEG C to form a water absorption mesh and obtain an intermediate product; according to the intermediate product mass of 100 percent, adding 2.5-3 percent of sulfur, 0.5-1 percent of stearic acid, 3-5 percent of zinc oxide and 0.7-1.2 percent of thiol benzothiazole, and vulcanizing rubber by a mixing way at 140-145 DEG C and 14-15MPa to form a framework mesh, wherein within the range of room temperature to 80 DEG C, the framework mesh can absorb 5-30 times of water, slowly expands for 3-30 days, and needs two to three months for the complete expansion; and after water absorption, the framework mesh has the strength more than 20kPa. The diverting agent good depth arrangement, deformation and plugging capability.

Description

A kind of preparation method of high strength elastic slow-expansion water-absorption particle diverting agent

Technical field

The present invention relates to a kind of preparation method of high strength elastic slow-expansion water-absorption particle diverting agent, can be used for deep, highly aqueous field fluid diversion, improve water drive, gather drive, the displacement effect of surfactant flooding, combination flooding, improve oil recovery.

Background technology

Water drive is the main mining type in the most oil fields of China, and profile control is one of important technical of improving water drive, raising RF.Exploitation is early stage; The oil increasing precipitation effect that the WIW profile control obtains is remarkable, but along with the long-term injecting water oil field generally gets into the high water-cut development later stage, stratum ubiquity current advantage passage; Cause injecting the circulation of invalid injection of water or poor efficiency; Conventional profile control shutoff can not have been satisfied highly aqueous field to improving the needs of water driving technology, the carrying out of many rounds profile control, and conventional profile control yield potential is more and more lower.The deep profile controlling fluid diversion, increase substantially the water drive swept volume and become the important technology developing direction that maturing field further improves waterflood recovery efficiency factor.The particulate species material of the synthetic preparation in ground; Being widely used in highly aqueous field in recent years improves in the water driving technology; Mainly containing materials such as volume expansion grain, flexible particle, rubber grain with particulate species profile control diversion agent at present, profile control improves and is bringing into play different effects in the water driving technology in the highly aqueous field of different condition.

Volume expansion grain has been brought into play vital role in deep profile controlling in recent years, and obtains widespread use, and the rig-site utilization in domestic most oil fields has all obtained good result.But because its water-swelling speed is fast, existing problems aspect the injection degree of depth; In addition, volume expansion grain suction back intensity is low, pump annotate and migration process in be prone to brokenly, be unfavorable for that the deep places and shutoff, make its in highly aqueous field the WIW deep profile controlling to improve the water drive effect limited; Domestic researchist once attempted the swollen particulate absorption speed of delay body, but did not all obtain substantial progress.

Flexible particle; Though have good pliable and tough deformation nature, there is not the swollen performance of water-absorbing body, ground ready-formed particle size makes it be difficult to realize real deep placement; And its product suspension liquid barreled causes transportation trouble, freight charges height, and shutoff unit's porous material valency height causes its consumption limited.

Mostly rubber grain is that junked tire utilizes again, and the cost of material is low but density high, do not absorb water, indeformable, injects the migration difficulty, can not realize that the deep places, and is difficult to realize deep fluid diversion purpose.

Summary of the invention

The objective of the invention is to be directed against deficiencies such as conventional volume expansion grain water-swelling excessive velocities, the low easy fragmentation of the swollen back of body intensity, deep placement difficulty improves.On the swollen particle of substance basis, pass through Molecular Structure Design; In the swollen network structure of conventional water-absorbing body; Introduce the macromolecule network of control absorption speed, thereby form the interpenetrating(polymer)networks three-dimensional structure material that possessing slow swollen, the overall characteristic such as intensity is high, performance is adjustable of suction, make its absorption speed before getting into earth formation deep slow; Can realize deep placement truly; HS after the deep formation water-absorbing body is swollen makes it have good shutoff steering qualities, thereby has overcome the deficiency of the swollen granule technology means of substance effectively, and the enforcement that improves the waterflood efficiency technology for the deep fluid diversion provides material conditions.

The present invention mainly provides a kind of employing polymer network IPN technology, the method for the slow swollen high-strength absorbing particulate material of preparation.

Polymer network IPN technology makes the suction network and the back bone network of material realize " pressure is dissolved each other "; The suction network provides water absorbing properties; Back bone network in order to the control absorption speed, improve the strength of materials, thereby guarantee that material had both had the ability of slow water-swelling, had enough intensity again.

Material adopts two-step approach synthetic:

The first step; By total mass 100%; Get monomer 10-20%, initiator 0.5-1%, linking agent 0.01-0.1% and tree elastomer 30-50% or/and speed control agent 0.1-1.0%, surplus is a water, at 40-80 ℃ cross-linking polymerization takes place down and forms the suction network; After the polymerization oven dry, obtain intermediate product 1;

Second step by intermediate product 1 quality 100%, added sulphur 2.5-3%, Triple Pressed Stearic Acid 0.5-1%, zinc oxide 3-5% and 2-thiol benzothiazole 0.7-1.2%, and at 140-145 ℃, 14-15MPa makes the vulcanization of rubber form back bone network through mixing;

Said monomer is one or more in acrylic amide, vinylformic acid, sodium acrylate, vinyl cyanide, the TEB 3K etc.

Said initiator is two kinds or several kinds of redox systems that form in hydrogen peroxide, ammonium persulphate, Potassium Persulphate, S-WAT, the ammonium bisulfite etc.

Said linking agent is a methene base bisacrylamide.

Said speed control agent is the Tripotassium iron hexacyanide.

The effect of invention

Routine suction volume expansion grain can absorb water 5-50 doubly in room temperature-80 ℃ scope, the initial stage suction is rapid, but expansion in general 30 minutes, and Young's modulus has only 2KPa even lower, is prone to broken in pump notes and the migration process; Flexible body does not then absorb water, body is not swollen.

The slow swollen particle of suction that the present invention is prepared, in room temperature-80 ℃ scope, the 5-30 that can absorb water doubly compares with conventional water-absorbing material, and the initial stage suction is slowly delayed swollen time 3-30 days, and the volumetric expansion that just absorbs water gradually behind the certain hour, expansion need 2-3 month; Suction back intensity is more than 10 times of the swollen particulate material of common aspect greater than 20KPa, is high-intensity resilient gel, has good deep placement, deformation and shut-off capacity.

Description of drawings

The slow swollen performance (TDS=2%) of the slow swollen high-strength absorbing particulate of Fig. 1.

Intensity (60 ℃) after the slow complete water-swelling of swollen high-strength absorbing particle of Fig. 2

Embodiment

Come further to set forth the particular content of invention below in conjunction with embodiment, provide the performance evaluation result of slow swollen high-strength particulate material.

Embodiment 1

Add 39.47g water, 10g acrylic amide, 0.5g hydrogen peroxide and ammonium persulphate, 0.03g methene base bisacrylamide, 50g tree elastomer successively under in the 250mL reaction vessel, stirring; After the logical nitrogen deoxygenation reaction vessel is sealed in 80 ℃ of following reactions and obtained the solid gums block product in 3 hours, vacuum-drying obtains intermediate product.

Through mixing, in the 100g midbody, add 3g sulphur, 1g Triple Pressed Stearic Acid, 5g zinc oxide, 1.292-thiol benzothiazole.At 140 ℃, the 14MPa sulfuration is delayed swollen high-strength absorbing particulate material with promptly getting after the product pulverizing.

Embodiment 2

Add 49.25g water, 15g vinylformic acid and sodium acrylate, 0.7g ammonium persulphate and Potassium Persulphate, 0.05g methene base bisacrylamide, 35g natural rubber latex successively under in the 250mL reaction vessel, stirring; After the logical nitrogen deoxygenation reaction vessel is sealed in 60 ℃ of following reactions and obtained the solid gums block product in 8 hours, vacuum-drying obtains intermediate product.

Through mixing, in the 100g midbody, add 2.8g sulphur, 0.7g Triple Pressed Stearic Acid, 4.5g zinc oxide, 1.0g2-thiol benzothiazole.At 143 ℃, the 15MPa sulfuration is delayed swollen high-strength absorbing particulate material with promptly getting after the product pulverizing

Embodiment 3

Add 37.9g water, 10g vinyl cyanide and TEB 3K, 1.0g S-WAT and ammonium bisulfite, 0.1g methene base bisacrylamide, 50g natural rubber latex, the 1.0g Tripotassium iron hexacyanide successively under in the 250mL reaction vessel, stirring; After the logical nitrogen deoxygenation reaction vessel is sealed in 40 ℃ of following reactions and obtained the solid gums block product in 24 hours, vacuum-drying obtains intermediate product.

Through mixing, in the 100g midbody, add 2.5g sulphur, 0.3g Triple Pressed Stearic Acid, 3g zinc oxide, 0.7g2-thiol benzothiazole.At 145 ℃, the 15MPa sulfuration is delayed swollen high-strength absorbing with promptly getting after the product pulverizing

Embodiment 4

This instance is used for explaining the intensity after slow swollen high-strength absorbing particulate delays swollen performance and expansion.

To delay swollen particulate samples and be placed in the simulation salt solution, take out the weighing quality at set intervals, calculate water absorbent rate, paint time-the water absorbent rate curve, see Fig. 1.Contrasted the speed of expansion of conventional water-absorbing material simultaneously.

After the complete water-swelling of material, measure its intensity, represent, see Fig. 2 with Young's modulus.

It is thus clear that the same terms, the suitable swollen multiple material of body, conventional water-absorbing material be with after water contact, water-swelling rapidly, expansion basically after 1.2 hours.And slow swollen high-strength absorbing material absorbs water slowly in the early stage, and 7 days just begin later on to expand gradually, and expansion is greatly about about 3 months.Behind the essentially identical multiple that expands, to compare with conventional water-absorbing material, slow swollen high-strength absorbing material has kept high intensity, is the former about 10 times.

Claims (1)

1. the preparation method of a high strength elastic slow-expansion water-absorption particle diverting agent; It is characterized in that: the first step, by total mass 100%, get monomer 10-20%, initiator 0.5-1%, linking agent 0.01-0.1%, emulsus tree elastomer 30-50% and speed control agent 0.1-1.0%; Surplus is a water; At 40-80 ℃ cross-linking polymerization taking place down and form the suction network, after the polymerization oven dry, obtains intermediate product 1;

Second step by intermediate product 1 quality 100%, added sulphur 2.5-3%, Triple Pressed Stearic Acid 0.5-1%, zinc oxide 3-5% and 2-thiol benzothiazole 0.7-1.2%, and at 140-145 ℃, 14-15MPa makes the vulcanization of rubber form back bone network through mixing;

Monomer is one or more of acrylic amide, vinylformic acid, sodium acrylate, vinyl cyanide, TEB 3K;

Initiator is two kinds or several kinds of redox systems that form of hydrogen peroxide, ammonium persulphate, Potassium Persulphate, S-WAT, ammonium bisulfite;

Linking agent is a methene base bisacrylamide;

The speed control agent is the Tripotassium iron hexacyanide.

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