CN103408703A - Liquid polymeric microspheres and synthetic method thereof - Google Patents
Liquid polymeric microspheres and synthetic method thereof Download PDFInfo
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- CN103408703A CN103408703A CN2013103397691A CN201310339769A CN103408703A CN 103408703 A CN103408703 A CN 103408703A CN 2013103397691 A CN2013103397691 A CN 2013103397691A CN 201310339769 A CN201310339769 A CN 201310339769A CN 103408703 A CN103408703 A CN 103408703A
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Abstract
The invention discloses liquid polymeric microspheres and a synthetic method thereof. The liquid polymeric microspheres comprise the following raw materials in mass part of 100 parts: 15-20 parts of AM, 15-20 parts of modified starch, 2-4 parts of APG and the balance of water. The synthetic method comprises the following steps: after the modified starch is dissolved, adding and dissolving completely AM and APG to prepare a reaction liquid; adding an initiator solution into the reaction liquid in 2-5 times, performing centrifugal separation, taking a cross-linked polymer at the lower layer, drying the cross-linked polymer to acquire colloid blocks; soaking the colloid blocks in saturated salt water continuously, grinding the colloid blocks into powder as per diameter of required microspheres, and meanwhile adding saturated salt water, so as to acquire the liquid polymeric microsphere finally. The liquid polymeric microspheres can be freely matched with anions, non-ions, cations and the like of a drilling fluid, can expand when reacting with water, has great expansion capacity, great crack plugging capability, excellent temperature resistance, excellent salt tolerance, can shrink when reacting with oil, can perform return discharge and blockage elimination automatically during well completion test, and is low in cost, non-toxic, pollution-free and biodegradable.
Description
Technical field
The present invention relates to a kind of formula be used in the drilling and completing fluids additive in oil-field development, be particularly related to a kind of liquid polymers microballoon and synthetic method thereof, can shutoff stratum microfracture, prevent the clever active microsphere grain of drilling fluid leakage, also can be used in water plugging and profile controlling.
Technical background
The main task of drilling well and directly purpose be that a good oil gas communicating passage is set up in reservoir and ground, but when oil and gas reservoir left by brill, drilling process itself can be broken the original equilibrium state of hydrocarbon-bearing pool, causes inevitable injury, is summed up, hurtful major cause has: at first, the intrusion of liquid phase and solid phase, the solid phase in drilling fluid, as with slurry soil, drilling cuttings, treatment agent insolubles, under the drilling well positive pressure differential drives, enter reservoir, stop up the oil gas flow passage; Liquid phase in drilling fluid is infiltrated reservoir pore space, causes water-sensitive, water lock or wettability reversal infringement.Secondly, the variation of pressure and temperature, can break the original balance of reservoir, may cause scale damage and Jia Min infringement or polyphasic flow effect.Net result causes Oil & Gas Productivity to descend and recovery ratio reduces.This also is unfavorable for improving Oil/gas Well output, improves the rate of oil and gas recovery not only bad for finding show of oil and gas (SO&G).For this reason, when productive zone left by brill, must take to prevent the drilling technique of oil and gas reservoir injury.
The first that is the contact oil and gas reservoir due to drilling fluid enters well working fluid, the quality of property of drilling fluid, especially with the compatibleness of oil and gas reservoir, directly affect the oil gas well capacity.It is found that; some oil reservoirs are after boring completion; output is also so high unlike expection, and obviously, this is owing to boring in Completion Operations; oil reservoir is by the contamination of working fluid; crack is stopped up by the degree of depth, thereby the resistance to flow increase is caused, and the key that prevents the oil and gas reservoir infringement is the drilling liquid technology of protection hydrocarbon zone; the research of the drilling fluid plugging material character therefore, reservoir shielded has great importance.
Technical measures commonly used in actual production at present are to add multiple plugging material; synergy improves the leak-off building capacity, reduces drilling fluid liquid phase and solid invasion hydrocarbon zone, reaches the purpose of protection reservoir; existing reservoir protection agent is of a great variety; the mechanism of action is different, and the scope of application is also different, but limitation is arranged; be mainly manifested in heat and salinity tolerance poor; affect property of drilling fluid, the liquid polymers microspherulite diameter that shutoff is synthesized is even, and expansion effect is good.Limited, act on singlely, environment is had to harm etc.
Summary of the invention
In order to overcome the defect of above-mentioned technology, the object of the present invention is to provide a kind of performance, protection of the environment that can be added in drilling fluid, improve drilling fluid, also can be used on a kind of liquid polymers microballoon and synthetic method thereof in water plugging and profile controlling, can be widely used in various drilling fluids, with drilling fluid-negatively charged ion, nonionic, positively charged ions etc. freely mate; Microspherulite diameter is 50-500um; Automatic screening enters formation fracture, and water-swellable is met oil and shunk; In preparation process, add promoting agent, make it also have the water of disappearing lock effect, promoting agent can adsorb at water-oil interface, can effectively reduce oil water interfacial tension, make the oil accumulation disperseed become the oil band, and constantly enlarge, thereby improve the displacement efficiency that injects fluid, displacement of reservoir oil effect is arranged; Anti-shear ability is good, is difficult for deforming, and shut-off capacity is good; Preparation is simple, easy to operate, can realize online injection.
In order to achieve the above object, technical scheme of the present invention is achieved in that
A kind of liquid polymers microballoon, its feed composition comprises by the mass fraction of 100 parts: AM15-20 part, treated starch 15-20 part, APG2-4 part, all the other are water;
Described AM is acrylamide;
Described treated starch is sulfonated starch.
Described APG is alkyl-glucoside.
A kind of synthetic method of liquid polymers microballoon:
Step 1, get treated starch 15-20 part water and fully dissolve after, add AM15-20 part, APG2-4 part fully to dissolve, make reaction solution,
Step 2, with initiator and water by volume for 0.3%-0.5% is mixed with initiator solution, initiator is N, N-dimethyl bisacrylamide and ammonium persulphate 1:1 in mass ratio are made into,
Step 3, initiator solution is joined in reaction solution minute 2-5 time, making the massfraction of initiator in reaction solution is 0.3%-1%, and centrifugation after reaction 3-5h under 50 ℃, take off a layer cross-linked polymer, dry after with saturated brine, cleaning, obtain micro-brown blob of viscose;
Step 4, the blob of viscose obtained continue to soak in saturated brine, blob of viscose is broken into to the fritter that can put into pulverizer, diameter according to required microballoon, with LG-160 type continuous dosing pulverizer the colloidal mill powdered, pulverize and add simultaneously saturated brine, the mass ratio of saturated brine and powder is 1.5:1, finally obtains a kind of liquid polymers microballoon.
The mechanism of action of the present invention is:
The present invention forms the particle shutoff in crack leakage place automatically along with drilling fluid enters stratum, and water-swellable is met oil and shunk.Contain the high-performance activeconstituents, wherein bioactive molecule is a kind of intermediate wet agent (according to a kind of extraordinary bio-surfactant of lithology selection), clever ball in crack is met water and is automatically discharged bioactive molecule, rock surface is converted into medium wetting, wetting angle θ is 90 °, make capillary resistance close to 0, can effectively eliminate water lock effect, gas lock effect or Jamin effect infringement, reduce to greatest extent oil flow resistance.
The present invention has following outstanding advantages:
1) swelling capacity is good, and clever ball is after meeting water 48h, and expansion multiple can reach 14 times.
2) shutoff crack ability is good, can reach 14MPa, and the plugged zone intensity of formation is high.
3) good stability, this particulate has good swelling capacity, sealing characteristics under the condition of high temperature (can reach 160 ℃), high salinity (unrestricted).
4) when the leakage crack occurring, clever ball is met water and automatically in crack leakage place, is formed shutoff.
5) be filled in the ball in crack, also can automatically discharge bioactive molecule after chance water, can effectively eliminate water lock effect, gas lock effect or Jamin effect infringement, reduce to greatest extent oil flow resistance.
6) this clever ball can be met oil and shunk, during the completion formation testing, can return voluntarily mediate stifled.
7) this clever ball low cost, nontoxic pollution-free, biodegradable.
Embodiment
Embodiment mono-
A kind of liquid polymers microballoon, its components in mass portion number comprises: AM accounts for 15 parts, and treated starch accounts for 15 parts, and APG accounts for 2 parts, 68 parts, water.
Described AM is acrylamide.
Described treated starch is sulfonated starch.
Described APG is alkyl-glucoside.
A kind of synthetic method of liquid polymers microballoon:
Step 1, get 15 portions of waters of treated starch and fully dissolve after, add AM15 part, APG2 part is fully dissolved, and makes reaction solution,
Step 2, be 0.3% to be mixed with initiator solution by volume with initiator and water, initiator is N, and N-dimethyl bisacrylamide and ammonium persulphate 1:1 in mass ratio are made into,
Step 3, initiator solution is joined in reaction solution, making the massfraction of initiator in reaction solution is 0.3% minutes for 3 times, and centrifugation after reaction 5h under 50 ℃, take off a layer cross-linked polymer, dry after with saturated brine, cleaning, and obtains micro-brown blob of viscose;
Step 4, the blob of viscose obtained continue to soak in saturated brine, blob of viscose is broken into to the fritter that can put into pulverizer, diameter according to required microballoon, with LG-160 type continuous dosing pulverizer the colloidal mill powdered, pulverize and add simultaneously saturated brine, the mass ratio of saturated brine and powder is 1.5:1, finally obtains a kind of liquid polymers microballoon.
Synthetic liquid polymers microspherulite diameter is even, and expansion effect is good.
Embodiment bis-
A kind of liquid polymers microballoon, its components in mass portion number comprises: AM accounts for 20 parts, and treated starch accounts for 15 parts, and APG accounts for 2 parts, 63 parts, water.
Described AM is acrylamide.
Described treated starch is sulfonated starch.
Described APG is alkyl-glucoside.
A kind of synthetic method of liquid polymers microballoon:
Step 1, get 15 portions of waters of treated starch and fully dissolve after, add AM20 part, APG2 part is fully dissolved, and makes reaction solution,
Step 2, be 0.3% to be mixed with initiator solution by volume with initiator and water, initiator is N, and N-dimethyl bisacrylamide and ammonium persulphate 1:1 in mass ratio are made into,
Step 3, initiator solution is joined in reaction solution, making the massfraction of initiator in reaction solution is 0.3% minutes for 2 times, and centrifugation after reaction 5h under 50 ℃, take off a layer cross-linked polymer, dry after with saturated brine, cleaning, and obtains micro-brown blob of viscose;
Step 4, the blob of viscose obtained continue to soak in saturated brine, blob of viscose is broken into to the fritter that can put into pulverizer, diameter according to required microballoon, with LG-160 type continuous dosing pulverizer the colloidal mill powdered, pulverize and add simultaneously saturated brine, the mass ratio of saturated brine and powder is 1.5:1, finally obtains a kind of liquid polymers microballoon.
Synthetic liquid polymers microspherulite diameter is even, and expansion effect is good.
Embodiment tri-
A kind of liquid polymers microballoon, its components in mass portion number comprises: AM accounts for 15 parts, and treated starch accounts for 20 parts, and APG accounts for 2 parts, 63 parts, water.
Described AM is acrylamide.
Described treated starch is sulfonated starch.
Described APG is alkyl-glucoside.
A kind of synthetic method of liquid polymers microballoon:
Step 1, get 20 portions of waters of treated starch and fully dissolve after, add AM15 part, APG2 part is fully dissolved, and makes reaction solution,
Step 2, be 0.3% to be mixed with initiator solution by volume with initiator and water, initiator is N, and N-dimethyl bisacrylamide and ammonium persulphate 1:1 in mass ratio are made into,
Step 3, initiator solution is joined in reaction solution, making the massfraction of initiator in reaction solution is 0.5% minutes for 5 times, and centrifugation after reaction 3h under 50 ℃, take off a layer cross-linked polymer, dry after with saturated brine, cleaning, and obtains micro-brown blob of viscose;
Step 4, the blob of viscose obtained continue to soak in saturated brine, blob of viscose is broken into to the fritter that can put into pulverizer, diameter according to required microballoon, with LG-160 type continuous dosing pulverizer the colloidal mill powdered, pulverize and add simultaneously saturated brine, the mass ratio of saturated brine and powder is 1.5:1, finally obtains a kind of liquid polymers microballoon.
Synthetic liquid polymers microspherulite diameter is even, and expansion effect is good.
Embodiment tetra-
A kind of liquid polymers microballoon, its components in mass portion number comprises: AM accounts for 20 parts, and treated starch accounts for 20 parts, and APG accounts for 2 parts, 58 parts, water.
Described AM is acrylamide.
Described treated starch is sulfonated starch.
Described APG is alkyl-glucoside.
A kind of synthetic method of liquid polymers microballoon:
Step 1, get 20 portions of waters of treated starch and fully dissolve after, add AM20 part, APG2 part is fully dissolved, and makes reaction solution,
Step 2, be 0.4% to be mixed with initiator solution by volume with initiator and water, initiator is N, and N-dimethyl bisacrylamide and ammonium persulphate 1:1 in mass ratio are made into,
Step 3, initiator solution is joined in reaction solution, making the massfraction of initiator in reaction solution is 0.5% minutes for 5 times, and centrifugation after reaction 4h under 50 ℃, take off a layer cross-linked polymer, dry after with saturated brine, cleaning, and obtains micro-brown blob of viscose,
Step 4, the blob of viscose obtained continue to soak in saturated brine, blob of viscose is broken into to the fritter that can put into pulverizer, diameter according to required microballoon, with LG-160 type continuous dosing pulverizer the colloidal mill powdered, pulverize and add simultaneously saturated brine, the mass ratio of saturated brine and powder is 1.5:1, finally obtains a kind of liquid polymers microballoon.
Synthetic liquid polymers microspherulite diameter is even, and expansion effect is good.
Claims (2)
1. liquid polymers microballoon, its feed composition comprises by the mass fraction of 100 parts: AM15-20 part, treated starch 15-20 part, APG2-4 part, all the other are water;
Described AM is acrylamide;
Described treated starch is sulfonated starch;
Described APG is alkyl-glucoside.
2. based on the synthetic method of weighing 1 described a kind of liquid polymers microballoon:
Step 1, get treated starch 15-20 part water and fully dissolve after, add AM15-20 part, APG2-4 part fully to dissolve, make reaction solution,
Step 2, with initiator and water by volume for 0.3%-0.5% is mixed with initiator solution, initiator is N, N-dimethyl bisacrylamide and ammonium persulphate 1:1 in mass ratio are made into,
Step 3, initiator solution is joined in reaction solution minute 2-5 time, making the massfraction of initiator in reaction solution is 0.3%-1%, and centrifugation after reaction 3-5h under 50 ℃, take off a layer cross-linked polymer, dry after with saturated brine, cleaning, obtain micro-brown blob of viscose;
Step 4, the blob of viscose obtained continue to soak in saturated brine, blob of viscose is broken into to the fritter that can put into pulverizer, diameter according to required microballoon, with LG-160 type continuous dosing pulverizer the colloidal mill powdered, pulverize and add simultaneously saturated brine, the mass ratio of saturated brine and powder is 1.5:1, finally obtains a kind of liquid polymers microballoon.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104533361B (en) * | 2014-12-15 | 2017-02-08 | 中国石油天然气股份有限公司 | Recycling and reutilization method for polymer flooding well returned materials |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101892037A (en) * | 2010-07-19 | 2010-11-24 | 中国海洋石油总公司 | Novel salt-resistant gel selective water shutoff agent |
| CN102304200A (en) * | 2011-05-27 | 2012-01-04 | 中国海洋石油总公司 | Crosslinked polymer microspheres and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101892037A (en) * | 2010-07-19 | 2010-11-24 | 中国海洋石油总公司 | Novel salt-resistant gel selective water shutoff agent |
| CN102304200A (en) * | 2011-05-27 | 2012-01-04 | 中国海洋石油总公司 | Crosslinked polymer microspheres and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104533361B (en) * | 2014-12-15 | 2017-02-08 | 中国石油天然气股份有限公司 | Recycling and reutilization method for polymer flooding well returned materials |
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Effective date of registration: 20181122 Address after: Room A 404, Xindu Building Materials Business Building, Beiyi Road, Dongying City, Shandong Province Patentee after: Dongying Suncoo Petroleum Co., Ltd. Address before: No. 18, two east section of electronic two road, Shaanxi, Shaanxi Patentee before: Xian Petroleum Univ. |
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