CN105602535A - Nanometer blocking agent for organic salt drilling fluid and preparation method of nanometer blocking agent - Google Patents
Nanometer blocking agent for organic salt drilling fluid and preparation method of nanometer blocking agent Download PDFInfo
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- CN105602535A CN105602535A CN201610142877.3A CN201610142877A CN105602535A CN 105602535 A CN105602535 A CN 105602535A CN 201610142877 A CN201610142877 A CN 201610142877A CN 105602535 A CN105602535 A CN 105602535A
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- drilling fluid
- organic salt
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- salt drilling
- sealing agent
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating
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Abstract
The invention discloses a nanometer blocking agent for organic salt drilling fluid and a preparation method of the nanometer blocking agent. The nanometer blocking agent for the organic salt drilling fluid is inorganic and organic hybrid copolymer formed by conducting drying treatment after co-polymerizing 1-8 parts by weight of methyl-methacrylate-based cage-like oligomerization silsesquioxane, 5-15 parts by weight of N-isopropylacrylamide and 14-22 parts by weight of acrylamide under the effect of an initiator. The nanometer blocking agent is adjustable in size, and has good temperature resistance, salt resistance and thermo-sensitivity, inorganic particles are evenly distributed in organic molecular chains, after entering a stratum pore throat, the inorganic particles and a stratum can be more tightly connected through the organic molecular chains, the inorganic particles can be more tightly connected through the organic molecular chains, material falling is avoided, and a good blocking effect is achieved.
Description
Technical field
The present invention relates to petroleum gas field, relate to particularly a kind of organic salt drilling fluid nanometer sealing agent and preparation thereofMethod.
Background technology
In drilling process, the transmission of mud shale pore pressure is the major reason that causes borehole well instability. Therefore, maintain the borehole wall steadyFixed key is to stop pore pressure transmission, stop pore pressure transmission must strengthen to micropore, microcrack effectivelyShutoff. Part mud shale has extremely low permeability and minimum pore throat size, and traditional sealing agent is difficult to its surperficial shapeBecome effective mud cake to stop liquid phase to be invaded, only have effectively shutoff pore throat of micro/nano level particle, stop liquid phase intrusivelyLayer, safeguards wellbore stability.
The huge specific area of nano material can be carried a large amount of functional groups and be met special functional requirement, nanoparticleThe size (more much smaller than stratum pore throat) that son is minimum, very easily enters micropore, stratum, can produce physics envelope to surface of stratumBlock up and clay surfaces externally and internally is produced to effective Chemical Inhibition, eliminating the interaction between stratum and drilling fluid, reducing stratumThe destruction of construction unit or distortion, increase opposing cave-in and produce the ability in crack, widened ' Safe Density Windows,In macroscopic view, strengthen borehole wall stability.
At present, abroad successfully nanometer technology is applied in drilling fluid field, they are by nano silicon, nanometer oxygenChange that the nano particle such as magnesium directly uses or surface modification after as sealing agent use, but in this kind of method nano inorganic particle andSurface organic molecule segment is the combination in macroscopic view, and sealing agent rigidity is larger, enter after the pore throat of stratum, particle and stratum,Loose contact between particle and particle, easily departs from again, affects plugging effect.
Cage shape polyhedral oligomeric silsesquioxane (POSS) is a kind of novel nano structural material occurring in recent years, be by-Si-O-forms inner inorganic skeleton, is externally connected to the nanoscale three dimensiona structure system of machine group. POSS base hybrid materialIn short period in the past, obtained development rapidly, the distinguishing feature that this class hybrid material has is: the three-dimensional knot of POSSThe equal portability substituted radical of each drift angle of structure, can make this inorganic nano material of POSS and organic molecule realize real meaningCombination on the molecular level of justice, like this, multi-functional POSS material is just as the crosslinking points quilt of a nano-scaleBe wrapped in each strand. Using such material as sealing agent, compared with traditional modified manometer silicon dioxide, POOSBe uniformly distributed with organic molecule chain, POSS is wrapped in organic molecule chain, enter after the pore throat of stratum, POSS particle withBetween stratum, POSS particle and POSS particle, can be connected more closely by organic molecule chain, prevent that material from coming off, increaseStrong plugging effect.
Organic salt drilling fluid is the one of water-base drilling fluid, and its feature is that salt content is high, has strong inhibition capability, oil-gas LayerProtect the advantages such as effective, be suitable for the construction of the Holes of Complicated Wells such as horizontal well, extended reach well. But organic salt drilling fluid meanwhile,High salinity also inorganic agent has been proposed to higher anti-salt requirement. The stereoeffect rigidity of POSS is strong, volume is large,After being combined with organic molecule, can improve whole macromolecular anti-salt and temperature resistance ability, can be used as sealing agent at organic salt drilling fluidMiddle use.
Summary of the invention
The object of this invention is to provide a kind of organic salt drilling fluid nanometer sealing agent material and preparation method thereof, have to improveThe shutoff caving-preventing ability of machine salt drilling fluid.
The present invention is achieved through the following technical solutions:
A kind of organic salt drilling fluid nanometer sealing agent is to be made up of the raw material that comprises following mass parts:
Methyl methacrylate base cage shape oligomeric silsesquioxane 1-8,
NIPA 5-15,
Acrylamide 14-22.
The preparation method of nanometer sealing agent for this organic salt drilling fluid, comprises the steps:
Described methyl methacrylate base cage shape oligomeric silsesquioxane, NIPA and acrylamide are addedEnter in deionized water, stir; Be heated to 50-60 DEG C, under nitrogen protection, slowly add initator, reaction4-6 hour, obtains glue, then dries and pulverizes, and obtains described organic salt drilling fluid nanometer sealing agent.
In above-mentioned preparation method, the deionized water adding and the mass parts of initator are as follows:
Deionized water: 55-80,
Initator: 0.05-2.
Described initator is selected from following any one or two or more mixtures: ammonium persulfate, potassium peroxydisulfate, azoDiisobutyl amidine dihydrochloride, preferably azo diisobutyl amidine dihydrochloride.
Organic salt drilling fluid provided by the invention with the beneficial effect of nanometer sealing agent is:
1, described organic salt drilling fluid is adjustable by nanometer sealing agent size, has good plugging effect. Methacrylic acidThe agent structure of carbomethoxy cage shape oligomeric silsesquioxane is oligomeric silsesquioxane, and it is hexahedron nanostructured, can enterThe micropore and the microcrack that enter stratum play plugging effect. By the methyl methacrylate base on eight drift angles, metering systemAcid carbomethoxy cage shape oligomeric silsesquioxane combines with NIPA and acrylamide, methyl methacrylateBase cage shape oligomeric silsesquioxane is distributed evenly in macromolecular network structure as crosslinking points. With methacrylic acidThe increase of the content of carbomethoxy cage shape oligomeric silsesquioxane, crosslinking points increases, and whole macromolecular size can be from nanoscaleRise to micron order, be applicable to the gap of different pore size in shutoff stratum. Meanwhile, N-isopropyl acid amides and acrylamideStrand in all contain a large amount of amide groups, amide groups can with stratum in clay particle interact, make whole shutoffAgent is adsorbed in surface of stratum, prevents from coming off.
2, described organic salt drilling fluid has Thermo-sensitive with nanometer sealing agent. NIPA in strand byIn molecule, there are hydrophilic amide groups and hydrophobic isopropyl simultaneously, make its homopolymers there is temperature sensitivity, facingBelow boundary's solution temperature (40-65 DEG C), water-soluble, be convenient to prepare drilling fluid; More than critical-temperature, in macromolecular chainPolar group degree of hydration reduces, and hydrophobic segment is separated out from solution, produces in molecule and Interpolymer Association, is gel,Be combined the anti-collapse effect of rear further enhancing shutoff with methyl methacrylate base cage shape oligomeric silsesquioxane.
3, described organic salt drilling fluid has good temperature resistance and salt-resistance with nanometer sealing agent. Due to oligomeric silsesquioxaneThe cage structure rigidity of alkane is extremely strong, and volume is larger, and the large molecule of being made up of it is difficult for occurring under the environment of high temperature and high saltDecompose and strand roll up, therefore product has good temperature resistance and anti-salt effect, be particularly useful for organic salt drilling fluid withThe water-based drilling liquid system of the high salinitys such as saturated salt-water drilling fluid, the shut-off capacity of raising drilling fluid, strengthens wellbore stabilityProperty.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples. DescribedMethod is conventional method if no special instructions. In following each embodiment, described part is mass fraction. Described reactantAll can obtain from open commercial sources if no special instructions.
Embodiment 1
In the four-hole bottle that mechanical agitator is housed, add 1 part of methyl methacrylate base cage shape oligomeric silsesquioxane, 5Part NIPA and 14 parts of acrylamides, 80 parts of deionized waters, 60 DEG C stir; Under nitrogen protection,Slowly add 0.05 part of azo diisobutyl amidine dihydrochloride, 60 DEG C add thermal response 4 hours, obtain glue, and post-dryingPulverize, obtain described organic salt drilling fluid nanometer sealing agent, specific performance is listed in table 1 and table 2.
Embodiment 2
In the four-hole bottle that mechanical agitator is housed, add 5 parts of methyl methacrylate base cage shape oligomeric silsesquioxanes, 15Part NIPA and 15 parts of acrylamides, 65 parts of deionized waters, 60 DEG C stir; Under nitrogen protection,Slowly add 0.1 part of azo diisobutyl amidine dihydrochloride, 60 DEG C add thermal response 6 hours, obtain glue, then ovendry powerBroken, obtain described organic salt drilling fluid nanometer sealing agent, specific performance is listed in table 1 and table 2.
Embodiment 3
In the four-hole bottle that mechanical agitator is housed, add 7 parts of methyl methacrylate base cage shape oligomeric silsesquioxanes, 13Part NIPA and 20 parts of acrylamides, 60 parts of deionized waters, 50 DEG C stir; Under nitrogen protection,Slowly add 1 part of potassium peroxydisulfate, 50 DEG C add thermal response 4 hours, obtain glue, and then dry and pulverize, described in obtainingOrganic salt drilling fluid nanometer sealing agent, specific performance is listed in table 1 and table 2.
Embodiment 4
In the four-hole bottle that mechanical agitator is housed, add 8 parts of methyl methacrylate base cage shape oligomeric silsesquioxanes, 15Part NIPA and 22 parts of acrylamides, 55 parts of deionized waters, 50 DEG C stir; Under nitrogen protection,Slowly add 2 parts of ammonium persulfates, 50 DEG C add thermal response 4 hours, obtain glue, and then dry and pulverize, described in obtainingOrganic salt drilling fluid nanometer sealing agent, specific performance is listed in table 1 and table 2.
Adopt permeability shutoff instrument in organic salt drilling fluid system, to carry out with nanometer sealing agent described organic salt drilling fluidSealing characteristics is evaluated, and dosage is 2%, and sand table average pore size used is 5 microns.
Organic salt drilling fluid well slurry formula is: 400mLH2O+0.3％Na2CO3+ 2% bentonite in powder+0.15% xanthans+1.5Low adhesive aggregation anionic cellulose+2% of % modified starch+60% sodium formate+200% barite, above each component is with the quality of waterMeter.
Table 1. organic salt drilling fluid is the performance evaluation in organic salt drilling fluid with nanometer sealing agent
As can be seen from Table 1, described organic salt drilling fluid, all has with nanometer sealing agent in organic salt drilling fluidSealing characteristics preferably, wherein with embodiment 2 effect optimums.
In employing, press filtration is committed a breach of etiquette and described organic salt drilling fluid nanometer sealing agent is carried out to performance in the water base slurry of saturated salt is commentedValency, investigates its shutoff and heat and salinity tolerance effect by filter loss.
1) 350ml saturated brine is placed in to height and stirs cup, add 1.00gNaHCO3Evaluate soil with 35.00g, stir 20min,Centre at least stops to scrape wall twice. 24 ± 3 DEG C of curing in airtight condition 24h, obtain the water base slurry of saturated salt; Stir 20min, survey six speedAnd filter loss.
2) to filling the sealing agent that adds 1% in the goblet of base slurry, high-speed stirred 20min, measures performance under room temperature,Then drilling fluid is poured into 120 DEG C of aging 16h in ageing can, high-speed stirred 5min after taking out, measures its performance (in table 1).
Table 2. organic salt drilling fluid is the performance evaluation in the water base slurry of saturated salt with nanometer sealing agent
As can be seen from Table 2, described organic salt drilling fluid uses nanometer sealing agent in saturated brine, 120 DEG C of aging 16hAfter still there is less filter loss, the shutoff in saturated salt water slurry of described organic salt drilling fluid nanometer sealing agent is describedEffect excellence, wherein with embodiment 2 effect optimums.
Claims (5)
1. an organic salt drilling fluid nanometer sealing agent, is characterized in that: the nanometer shutoff of described organic salt drilling fluidAgent is to be formed by the material copolymerization that comprises following mass parts:
Methyl methacrylate base cage shape oligomeric silsesquioxane 1-8,
NIPA 5-15,
Acrylamide 14-22.
2. the preparation method of nanometer sealing agent for organic salt drilling fluid claimed in claim 1, is characterized in that, comprise asLower step:
Described methyl methacrylate base cage shape oligomeric silsesquioxane, NIPA and acrylamide are addedEnter in deionized water, stir; Then be heated to 50-60 DEG C, under nitrogen protection, slowly add initator,Reaction 4-6 hour, obtains glue, then dries and pulverizes, and obtains described organic salt drilling fluid nanometer sealing agent.
3. method according to claim 2, the addition of described deionized water and initator is counted by mass parts:
Deionized water: 55-80,
Initator: 0.05-2.
4. preparation method according to claim 3, described initator be selected from following any one or two or moreMixture: ammonium persulfate, potassium peroxydisulfate, azo diisobutyl amidine dihydrochloride, the preferred azo two of described initator is differentButyl amidine dihydrochloride.
5. an application process for nanometer sealing agent for organic salt drilling fluid adds 1-2% in organic salt drilling fluid well slurryOrganic salt drilling fluid claimed in claim 1 nanometer sealing agent.
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Cited By (7)
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| CN109233761A (en) * | 2018-11-09 | 2019-01-18 | 西南石油大学 | Modified Thermo-sensitive NIPAM bentonite and temperature response type drilling fluid |
| CN109705810A (en) * | 2018-12-13 | 2019-05-03 | 王鹏 | A kind of leakage protection agent of the high temperature and pressure circulatory system |
| CN110819325A (en) * | 2019-10-24 | 2020-02-21 | 北京大德广源石油技术服务有限公司 | Repeated fracturing temporary plugging agent and preparation method thereof |
| CN111423860A (en) * | 2020-05-21 | 2020-07-17 | 济南市坤鹏技术开发中心 | High-strength nano plugging agent |
| CN112812245A (en) * | 2021-01-25 | 2021-05-18 | 中国石油大学(华东) | High-temperature-resistant pressure-bearing plugging agent for water-based drilling fluid and preparation method and application thereof |
| CN114456325A (en) * | 2021-12-22 | 2022-05-10 | 中国石油天然气集团有限公司 | Hydrophobic membrane structure wall-fixing agent and preparation method and application thereof |
| WO2022268087A1 (en) * | 2021-06-22 | 2022-12-29 | 西南石油大学 | High-temperature-resistant silicon dioxide grafted tertiary amine nanoparticle plugging agent and water-based drilling fluid |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109233761A (en) * | 2018-11-09 | 2019-01-18 | 西南石油大学 | Modified Thermo-sensitive NIPAM bentonite and temperature response type drilling fluid |
| CN109705810A (en) * | 2018-12-13 | 2019-05-03 | 王鹏 | A kind of leakage protection agent of the high temperature and pressure circulatory system |
| CN110819325A (en) * | 2019-10-24 | 2020-02-21 | 北京大德广源石油技术服务有限公司 | Repeated fracturing temporary plugging agent and preparation method thereof |
| CN111423860A (en) * | 2020-05-21 | 2020-07-17 | 济南市坤鹏技术开发中心 | High-strength nano plugging agent |
| CN112812245A (en) * | 2021-01-25 | 2021-05-18 | 中国石油大学(华东) | High-temperature-resistant pressure-bearing plugging agent for water-based drilling fluid and preparation method and application thereof |
| CN112812245B (en) * | 2021-01-25 | 2022-05-10 | 中国石油大学(华东) | High-temperature-resistant pressure-bearing plugging agent for water-based drilling fluid and preparation method and application thereof |
| WO2022268087A1 (en) * | 2021-06-22 | 2022-12-29 | 西南石油大学 | High-temperature-resistant silicon dioxide grafted tertiary amine nanoparticle plugging agent and water-based drilling fluid |
| US11692121B2 (en) | 2021-06-22 | 2023-07-04 | Southwest Petroleum University | Tertiary amine-grafted silica nano-plugging agent and water-based drilling fluids |
| CN114456325A (en) * | 2021-12-22 | 2022-05-10 | 中国石油天然气集团有限公司 | Hydrophobic membrane structure wall-fixing agent and preparation method and application thereof |
| CN114456325B (en) * | 2021-12-22 | 2024-05-03 | 中国石油天然气集团有限公司 | Wall fixing agent with hydrophobic membrane structure and preparation method and application thereof |
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Effective date of registration: 20210204 Address after: 100007 No. 9 North Main Street, Dongcheng District, Beijing, Dongzhimen Patentee after: CHINA NATIONAL PETROLEUM Corp. Patentee after: CNPC Bohai Drilling Engineering Co.,Ltd. Address before: 300457 Tianjin Binhai New Area Development Zone Huanghai Road 106 Bohai Drilling Engineering Co., Ltd. science and Technology Development Office Patentee before: CNPC Bohai Drilling Engineering Co.,Ltd. |