CN111978939B - Polyion liquid used as surface hydration inhibitor and water-based drilling fluid system - Google Patents
Polyion liquid used as surface hydration inhibitor and water-based drilling fluid system Download PDFInfo
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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
- C09K8/04—Aqueous well-drilling compositions
- C09K8/14—Clay-containing compositions
- C09K8/18—Clay-containing compositions characterised by the organic compounds
- C09K8/22—Synthetic organic compounds
- C09K8/24—Polymers
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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
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F112/16—Halogens
- C08F112/18—Chlorine
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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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/5083—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated 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
- C09K2208/02—Spotting, i.e. using additives for releasing a stuck drill
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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
Abstract
The invention discloses a polyion liquid used as a surface hydration inhibitor and a water-based drilling fluid system. The inhibitor used by the water-based drilling fluid is polyion liquid, and the polyion liquid comprises thiazole compounds, 4-chloromethyl styrene, azo compounds and methanol as synthetic raw materials; the drilling fluid comprises the polyionic liquid. The polyion liquid is used as a surface hydration inhibitor, has good compatibility with drilling fluid, has excellent inhibition performance, can effectively inhibit the hydration expansion of shale gas shale, obviously reduces the shale expansion rate, and prevents borehole collapse, drilling sticking and the like, thereby strengthening the borehole stability and reducing the complex conditions in the well.
Description
Technical Field
The invention relates to the technical field of oil and gas field drilling, in particular to a polyion liquid serving as a surface hydration inhibitor and a water-based drilling fluid containing the same.
Background
The exploration and development of clean energy shale gas become important strategic tasks for guaranteeing the substitution of oil and gas resources in China at present. One of the key technologies for shale gas exploration and development is horizontal well drilling. The stability of shale in horizontal well sections and the instability of shale walls of conventional oil and gas wells have always been the most common and difficult problems to solve worldwide in drilling engineering. Drilling fluid technology is one of the key technologies to ensure rapid and safe drilling.
The drilling fluid systems commonly used at present are water-based drilling fluids and oil-based drilling fluids. The shale gas horizontal well section drilling fluid mainly adopts oil-based drilling fluid. The oil-based drilling fluid is a multiphase dispersion system in which organic soil is dispersed in oil as a continuous phase, so that the oil-based drilling fluid has the characteristics of good shale inhibition, stable well wall, good thermal stability, excellent lubricating property and the like. However, the high cost, high lost circulation and environmental requirements of oil-based drilling fluids limit the use of oil-based drilling fluids. However, the inhibition of surface hydration of mudstone or highly water sensitive shale formations by current stage water-based drilling fluids remains problematic. The essence of shale hydration is the hydration of clay minerals in shale. The hydration of the clay mineral is as follows: surface hydration and osmotic hydration. The commercial inhibitor at the present stage can inhibit osmotic hydration swelling and prolong the hydration time. For inhibiting the surface hydration, no targeted effective method exists at present, the clay mineral surface hydration is mainly inhibited by an activity balance principle, and the inhibition is generally realized by adopting saturated cesium formate and potassium formate, but the solubility of the saturated formate is very high. The use of large amounts of formate is not only expensive, but also has a severe impact on the rheology of the drilling fluid. Therefore, it is highly desirable to develop a new inhibitor to effectively improve the inhibition of water-based drilling fluids.
The ionic liquid is an organic salt in a liquid state composed of cations and anions at or near room temperature. The ionic liquid has many excellent properties, such as high thermal stability; the structure is designable, and the ionic liquid formed by combining different anions and cations has good solubility to inorganic salt, water and organic matters; no volatility, etc. Due to these special properties, ionic liquids exhibit incomparable advantages over conventional methods in many aspects such as organic synthesis, separation technology, electrochemistry, aerospace lubricants, heat storage materials, and the like, and some of them have been successfully applied in the industrial field. The polyion liquid is used as a surface hydration inhibitor and used for water-based drilling fluid to solve the problems of well wall stability, reservoir pollution and the like, is a key technology of shale gas drilling at present and is a development trend of shale drilling at home and abroad.
Disclosure of Invention
Aiming at the problem of borehole wall instability caused by the deficiency of the conventional inhibitor at present, the invention provides polyion liquid as a surface hydration inhibitor, which can effectively prevent shale from hydrating and expanding, thereby achieving the purpose of stabilizing the borehole wall. And a novel water-based drilling fluid which can be suitable for shale formation is developed to replace an oil-based drilling fluid, so that the problems of well wall stability, reservoir pollution and the like can be solved. In order to achieve the purpose, the technical scheme of the invention is as follows: a polyion liquid is used as a surface hydration inhibitor and a water-based drilling fluid system, the raw materials of the polyion liquid inhibitor comprise a thiazole compound, 4-chloromethyl styrene, an azo compound and methanol, and the polyion liquid inhibitor is prepared by the following steps:
synthesis of ionic liquid: respectively weighing 4-chloromethyl styrene and thiazole compounds, placing the 4-chloromethyl styrene and the thiazole compounds in a reactor, stirring for 1-2h, fully mixing the 4-chloromethyl styrene and the thiazole compounds, and then condensing and refluxing the mixture for 15-20h under the condition of heating and stirring at the temperature of 60-70 ℃. And naturally cooling to 20-30 ℃ after the reaction is finished, and repeatedly washing the product for 3-5 times by using 10-15mL of ethyl acetate to obtain the ionic liquid.
Synthesis of polyion liquid: respectively weighing the ionic liquid and the azo compound into a reactor, introducing inert gas nitrogen for 30-40min, adding 30-40mL of methanol into the reactor, stirring for 1-2h to ensure that 2 substances are fully contacted and mixed in the methanol, and then reacting for 24-30h under the condition of heating at 60-70 ℃ to finally obtain the polyion liquid.
The thiazole compound is one of 2-methylthiazole, 4-methylthiazole, 5-methylthiazole, 2, 4-dimethylthiazole, 2, 5-dimethylthiazole and 4, 5-dimethylthiazole;
the azo compound is one of azodiisobutyronitrile and azodiisoheptonitrile.
Another object of the present invention is to provide a water-based drilling fluid to which the polyionic liquid inhibitor of the present invention is added.
Based on the weight parts of water, the drilling fluid comprises the following components: 3 to 5 percent of clay, 1 to 5 percent of plugging agent, 0.5 to 2 percent of inhibitor, 0 to 300 percent of weighting agent, 0.5 to 1 percent of tackifier, 1 to 5 percent of lubricant, 1 to 5 percent of viscosity reducer, 1 to 5 percent of filtrate reducer and 1 to 5 percent of flocculant.
The clay comprises one or more of bentonite, sepiolite and attapulgite; the plugging agent is one or more of asphalt, sulfonated asphalt, nano silicon dioxide and nano barite; the surface hydration blocking agent is the polyion liquid inhibitor; the weighting agent is barite and/or iron ore powder; the tackifier is one or more of high-viscosity polycation cellulose, high-viscosity sodium carboxymethyl cellulose, acrylate and acrylamide copolymer and hydroxyethyl cellulose; the lubricant is plastic pellets and/or graphite; the adopted viscosity reducer comprises one or more of sulfomethyl tannin, sulfomethyl tannin extract, sulfonated styrene-maleic anhydride copolymer and vinyl acetate-maleic anhydride copolymer; the filtrate reducer is one or more of sodium carboxymethyl cellulose, lignite alkali liquor, sodium nitrohumate, chromium humic acid and carboxymethyl starch; the flocculating agent is one or more of acrylonitrile copolymer potassium salt, acrylamide and sodium acrylate copolymer and composite ionic macromolecular weight polymer.
The invention has the following beneficial effects:
the polyion liquid prepared by the invention is used as a surface hydration inhibitor, has strong inhibition effect on hydration expansion and dispersion of shale gas shale, can obviously reduce the shale expansion rate, prevent borehole collapse, stuck drilling and the like, strengthens the borehole stability and reduces the underground complex condition, and is an inhibitor with excellent performance.
The water-based drilling fluid is shale gas shale water-based drilling fluid, can effectively inhibit hydration expansion and dispersion of shale gas shale, reduces the expansion rate of shale, further can prevent borehole collapse and drill sticking, and can also strengthen borehole stability and reduce complex underground accidents.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. In the present examples, the parts are all parts by weight unless otherwise specified.
Example 1:
1. synthesis of polyion liquid inhibitor:
(1) synthesis of ionic liquid: respectively weighing 1.8g of 4-chloromethyl styrene and 1g of 2-methylthiazole, placing the 4-chloromethyl styrene and the 2-methylthiazole in a reactor, stirring for 1.5 hours to fully mix the 4-chloromethyl styrene and the 2-methylthiazole, and then condensing and refluxing the mixture for 16 hours under the condition of heating and stirring at the temperature of 60 ℃. And naturally cooling to 22 ℃ after the reaction is finished, and repeatedly washing the product for 3 times by using 12mL of ethyl acetate to obtain the ionic liquid.
(2) Synthesis of polyion liquid: weighing 2g of ionic liquid and 0.08g of azobisisobutyronitrile respectively, placing the ionic liquid and the azobisisobutyronitrile into a reactor, introducing inert gas nitrogen for 30min, adding 30mL of methanol into the reactor, stirring for 1.5h to ensure that the 2 substances are fully contacted and mixed in the methanol, and then reacting for 24h under the condition of heating at 60 ℃ to finally obtain the polyion liquid inhibitor 1.
2. Preparation of the water-based drilling fluid:
weighing 128g of deionized water, heating to 70 ℃, adding 4.0g of bentonite under 500r/min low-speed electric stirring, stirring for 10min, adding 2.0g of the polyion liquid inhibitor prepared in example 1, stirring for 10min, adding 2.6g of nano silicon dioxide, stirring for 10min, adding 3.6g of graphite, stirring for 10min, adding 2.8g of sulfomethyl tannin, mixing and stirring for 10min to obtain the water-based drilling fluid 1.
Example 2:
1. synthesis of polyion liquid inhibitor:
(1) synthesis of ionic liquid: 2.0g of 4-chloromethyl styrene and 1.3g of 5-methylthiazole are respectively weighed and placed in a reactor to be stirred for 1.8 hours to be fully mixed, and then the mixture is subjected to condensation reflux for 18 hours under the heating and stirring conditions of 65 ℃. And naturally cooling to 25 ℃ after the reaction is finished, and repeatedly washing the product for 5 times by using 14mL of ethyl acetate to obtain the ionic liquid.
(2) Synthesis of polyion liquid: 2.2g of ionic liquid and 0.1g of azobisisoheptonitrile are respectively weighed and placed in a reactor, 38mL of methanol is added into the reactor after inert gas nitrogen is introduced for 40min and stirred for 1.8h, so that 2 substances are fully contacted and mixed in the methanol, and then the mixture is reacted for 28h under the condition of heating at 65 ℃, and finally the polyion liquid inhibitor 2 is obtained.
2. Preparation of the water-based drilling fluid:
100g of deionized water is weighed, heated to 70 ℃, and stirred for 10min by adding 3.3g of sepiolite under the low-speed electric stirring of 500r/min, then 2.0g of the polyion liquid inhibitor prepared in the embodiment 2 is added and stirred for 10min, 2.5g of asphalt is added and stirred for 10min, 100.0g of iron ore powder is added and stirred for 10min, and finally 0.8g of light ethyl cellulose is added and stirred for 10min, so that the water-based drilling fluid 2 is obtained.
Example 3:
1. synthesis of polyion liquid inhibitor:
(1) synthesis of ionic liquid: 2.2g of 4-chloromethyl styrene and 1.4g of 2, 5-dimethyl thiazole are respectively weighed and placed in a reactor to be stirred for 2 hours to be fully mixed, and then the mixture is condensed and refluxed for 20 hours under the condition of heating and stirring at the temperature of 70 ℃. And naturally cooling to 30 ℃ after the reaction is finished, and repeatedly washing the product for 5 times by using 15mL of ethyl acetate to obtain the ionic liquid.
(2) Synthesis of polyion liquid: 2.6g of ionic liquid and 0.12g of azobisisoheptonitrile are respectively weighed and placed in a reactor, 40mL of methanol is added into the reactor after inert gas nitrogen is introduced for 40min and stirred for 2h, so that the 2 substances are fully contacted and mixed in the methanol, and then the mixture reacts for 30h under the condition of heating at 70 ℃, and finally the polyion liquid inhibitor 3 is obtained.
2. Preparation of the water-based drilling fluid:
120.0g of deionized water is weighed, heated to 70 ℃, and stirred for 10min by adding 3.8g of bentonite under 500r/min low-speed electric stirring, then 2.0g of the polyion liquid inhibitor prepared in the embodiment 3 is added, stirred for 10min, added with 3.0g of sulfonated asphalt, mixed and stirred for 10min, and the water-based drilling fluid 3 is obtained.
Example 4:
1. synthesis of polyion liquid inhibitor:
(1) synthesis of ionic liquid: 1.6g of 4-chloromethyl styrene and 1.2g of 4, 5-dimethyl thiazole are respectively weighed and placed in a reactor to be stirred for 1.6 hours to be fully mixed, and then the mixture is condensed and refluxed for 16 hours under the heating and stirring conditions of 66 ℃. And naturally cooling to 26 ℃ after the reaction is finished, and repeatedly washing the product for 4 times by using 12mL of ethyl acetate to obtain the ionic liquid.
(2) Synthesis of polyion liquid: respectively weighing the ionic liquid and the azo compound in a reactor, introducing inert gas nitrogen for 35min, adding 35mL of methanol into the reactor, stirring for 1.6h to fully contact and mix the 2 substances in the methanol, and then reacting for 26h under the condition of heating at 66 ℃ to finally obtain the polyion liquid inhibitor 4.
2. Preparation of the water-based drilling fluid:
100g of deionized water is weighed, the temperature is raised to 70 ℃, 4.6g of bentonite is added and stirred for 10min under the low-speed electric stirring of 500r/min, 2.0g of the polyion liquid inhibitor prepared in the embodiment 4 is added and stirred for 10min, 4.0g of nano barite is added and stirred for 10min, 4.0g of graphite is added and stirred for 10min, and finally 4.0g of sulfomethyl sodium hydrosol is added and mixed for 10min, so that the water-based drilling fluid 4 is obtained.
To further illustrate the effect of the polyionic liquid inhibitor prepared by the present invention in formulating a water-based drilling fluid, the shale expansion ratio determination experiment was conducted on the synthesized inhibitors of examples 1-4, and rheological property tests were conducted on water-based drilling fluid 1-water-based drilling fluid 4, respectively.
1. Shale expansion experiment
The polyionic liquid inhibitor added in the four examples was replaced with the polyionic liquid inhibitor added in the previous examples 1-4, respectively, and the polyionic liquid inhibitors were added in an amount of 0%, 0.5%, 1.0%, 1.5%, respectively, again based on the weight of water in each example, and the shale expansion tests were performed separately, the results of which are shown in table 1.
TABLE 1 shale expansion ratio
As can be seen from the shale expansion rates of examples 1-4 in Table 1, the polyion liquid inhibitor synthesized by the invention has excellent effect, can obviously inhibit the hydration expansion of shale gas shale, and can obviously reduce the shale expansion rate. And when the addition amount of the polyion liquid inhibitor is 1.0%, the inhibition effect is optimal, and the cost of the drilling fluid can be reduced.
2. Rheological property test of water-based drilling fluid
The rheological properties of the water-based drilling fluids prepared in examples 1 to 4 were tested, all the water-based drilling fluids were subjected to hot rolling at a temperature of 105 ℃ for 16h, and the rheological parameters before and after hot rolling were tested, with the test results shown in table 2.
TABLE 2 Water-based drilling fluid Performance parameters
As can be seen from the above table, the rheological parameters of the four polyion liquids prepared in example 1, example 2, example 3 and example 4 as surface hydration inhibitors are not changed greatly before and after hot rolling, which indicates that the synthesized inhibitor of the present invention has little influence on the rheological properties after being added into the drilling fluid. In addition, the YP/PV values of the water-based drilling fluid are all in the range of 0.36-0.48, the flow type of the drilling fluid in the annular space belongs to flat laminar flow, and the water-based drilling fluid is characterized by having higher rock carrying capacity under lower viscosity and having smaller scouring effect on the well wall, so that the water-based drilling fluid has good rheological property.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. The application of polyion liquid as a surface hydration inhibitor is characterized in that the polyion liquid inhibitor is prepared from thiazole compounds, 4-chloromethyl styrene, azo compounds and methanol by the following steps:
s1 synthesis of ionic liquid: respectively weighing 4-chloromethyl styrene and thiazole compounds, placing the 4-chloromethyl styrene and the thiazole compounds in a reactor, stirring for 1-2 hours, fully mixing the 4-chloromethyl styrene and the thiazole compounds, then condensing and refluxing the mixture for 15-20 hours under the heating and stirring condition of 60-70 ℃, naturally cooling the mixture to 20-30 ℃ after the reaction is finished, and repeatedly washing the product for 3-5 times by using 10-15mL ethyl acetate to obtain ionic liquid;
synthesis of S2 polyion liquid: respectively weighing the ionic liquid and the azo compound into a reactor, introducing inert gas nitrogen for 30-40min, adding 30-40mL of methanol into the reactor, stirring for 1-2h to ensure that 2 substances are fully contacted and mixed in the methanol, and then reacting for 24-30h under the condition of heating at 60-70 ℃ to finally obtain the polyion liquid.
2. The application of the polyion liquid as the surface hydration inhibitor according to claim 1, wherein in the step of synthesizing the S1 ionic liquid, the thiazole compound is one of 2-methylthiazole, 4-methylthiazole, 5-methylthiazole, 2, 4-dimethylthiazole, 2, 5-dimethylthiazole and 4, 5-dimethylthiazole; in the step of synthesizing the S2 polyion liquid, the azo compound is one of azobisisobutyronitrile and azobisisoheptonitrile.
3. The use of polyion liquid as surface hydration inhibitor according to claim 1, wherein in the step of synthesizing the S1 ionic liquid, the molar ratio of thiazole compound to 4-chloromethyl styrene is 1: 1 to 1.25; in the step of synthesizing the S2 polyion liquid, the addition amount of the azo compound is 2-5% of the weight of the ionic liquid.
4. A water-based drilling fluid, wherein the polyionic liquid according to any one of claims 1 to 3 is added as a surface hydration inhibitor.
5. The water-based drilling fluid of claim 4, wherein the drilling fluid comprises the following components: water, clay, blocking agent, surface hydration inhibitor, weighting agent, tackifier, lubricant, viscosity reducer, filtrate reducer and flocculant.
6. The water-based drilling fluid of claim 5, wherein the clay is added in an amount of 3-5%, the blocking agent is added in an amount of 1-5%, and the surface hydration inhibitor is added in an amount of 0.5-2% by weight of water contained in the water-based drilling fluid; the additive amount of the weighting agent is 0-300%, the additive amount of the tackifier is 0.5-1%, the additive amount of the lubricant is 1-5%, the additive amount of the viscosity reducer is 1-5%, the additive amount of the fluid loss additive is 1-5%, and the additive amount of the flocculating agent is 1-5%.
7. The water-based drilling fluid of claim 5, wherein the clay comprises one or more of bentonite, sepiolite and attapulgite; the plugging agent is one or more of asphalt, sulfonated asphalt, nano silicon dioxide and nano barite; the surface hydration blocking agent is the polyion liquid inhibitor; the weighting agent is barite and/or iron ore powder; the tackifier is one or more of high-viscosity polycation cellulose, high-viscosity sodium carboxymethyl cellulose, acrylate and acrylamide copolymer and hydroxyethyl cellulose; the lubricant is plastic pellets and/or graphite; the adopted viscosity reducer comprises one or more of sulfomethyl tannin, sulfomethyl tannin extract, sulfonated styrene-maleic anhydride copolymer and vinyl acetate-maleic anhydride copolymer; the filtrate reducer is one or more of sodium carboxymethyl cellulose, lignite alkali liquor, sodium nitrohumate, chromium humic acid and carboxymethyl starch; the flocculating agent is one or more of acrylonitrile copolymer potassium salt, acrylamide and sodium acrylate copolymer and composite ionic macromolecular weight polymer.
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