CN114805670B - Polymer brush lubricant for water-based drilling fluid and preparation method and application thereof - Google Patents
Polymer brush lubricant for water-based drilling fluid and preparation method and application thereof Download PDFInfo
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- C09K8/02—Well-drilling compositions
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Abstract
The invention provides a polymer brush lubricant for water-based drilling fluid, a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing and stirring short-chain acrylic ester, long-chain acrylic ester and polar acrylic ester uniformly, dissolving in base oil, and then adding a molecular weight regulator; under the nitrogen atmosphere, adding an initiator to react; and after the reaction is finished, naturally cooling to room temperature to obtain the polymer brush lubricant for the water-based drilling fluid. The lubricant provided by the invention has high-efficiency lubrication effect in different drilling fluid systems and well slurries, has good compatibility, can resist ultra-high temperature of 220 ℃, and still has excellent lubrication effect after aging at ultra-high temperature; the lubricant disclosed by the invention is nontoxic, easy to biodegrade, good in environmental protection performance and beneficial to improving the environmental protection performance of drilling fluid and the sustainable development level of oil-gas exploration and development.
Description
Technical Field
The invention relates to a polymer brush lubricant for water-based drilling fluid, a preparation method and application thereof, belonging to the field of oilfield chemistry in petroleum industry.
Background
In the field of oil and gas drilling, compared with conventional wells, unconventional wells such as ultra-long horizontal wells, cluster wells, large-displacement wells and the like have higher yield, recovery ratio and wider applicability, so that the quantity and specific gravity of the unconventional wells in oil and gas drilling are increased year by year. However, these wells are prone to problems such as collapse, sticking, bit balling, etc. during the drilling process. The problems of high friction and high torque in the drilling process are solved, and the method is a key of the current drilling process.
At present, the most effective method for reducing friction and torque of drilling fluid is to add drilling fluid lubricant into the drilling fluid so as to reduce friction coefficients of drill rods, sleeves, drilling tools and well walls and improve the lubricating performance of the drilling fluid. Currently, lubricants are of a wide variety and are classified into synthetic monomer types, which are mainly classified into: esters, alcohols, oils, emulsions, and the like. These monomers include low solubility alcohols, fatty acid esters, bio-oils, vegetable oils, and the like.
The lubricant for drilling fluid is required to have sufficient stability at high temperature and to exert its lubricating properties in the face of complex conditions downhole. Chinese patent document CN106833557A discloses a preparation method of a lubricant for drilling fluid, which takes vegetable oleic acid, an organic solvent, a condensing agent and alcohol amine as main reactants, and carries out synthesis reaction under certain temperature and time conditions, wherein the temperature resistance of an amide condensate containing alcoholic hydroxyl groups is up to 200 ℃, but the reaction process is longer, the experimental steps are more complex, and the lubrication effect under an ultra-high temperature environment is poor.
Polymer brushes, also known as polymer molecular brushes, refer to polymers having a high degree of grafting by grafting polymer molecular chains onto a polymer backbone at high density. When the grafting density of the branched chains is large enough, the branched chains extend outwards perpendicularly to the main chain of the polymer due to steric hindrance so as to avoid overlapping of the branched chains, thus the whole polymer molecule forms a brush-like configuration, and is different from a random coil conformation of a common polymer chain, and the physical and chemical properties of the polymer are different from those of the common polymer. The polymer brush may reduce the dynamic coefficient of friction of the surface by several orders of magnitude compared to an oil lubricated surface. Polymer brushes not only provide improved drag reduction efficiency, but also provide significant improvement in shear stability, but no related studies have been reported on the application of polymer brush lubricants to the drilling fluid field.
Currently, the existing lubricant for water-based drilling fluid has the defects that: (1) The high temperature resistance is insufficient, degradation and failure are easy to occur under the high temperature condition, and the drilling requirement of deep stratum cannot be met. (2) The environmental protection performance is poor, and the drilling requirements of the environment sensitive area can not be met.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a polymer brush lubricant for water-based drilling fluid, and a preparation method and application thereof. The polymer brush lubricant is prepared by polymerizing the acrylate monomer composition, has better performance in ultra-high temperature and high pressure environments, is nontoxic, harmless and environment-friendly, and overcomes the defect of insufficient high-temperature stability of the conventional lubricant for water-based drilling fluid.
The technical scheme of the invention is as follows:
a preparation method of a polymer brush lubricant for water-based drilling fluid comprises the following steps:
mixing and stirring short-chain acrylic ester, long-chain acrylic ester and polar acrylic ester uniformly, dissolving in base oil, and then adding a molecular weight regulator; under the nitrogen atmosphere, adding an initiator to react; and after the reaction is finished, naturally cooling to room temperature to obtain the polymer brush lubricant for the water-based drilling fluid.
According to the invention, the short-chain acrylic ester is one or more than two of methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate and propyl-2-methyl-2-acrylic ester.
According to the present invention, the long-chain acrylic ester is preferably one or a combination of two or more of dodecyl 2-acrylate (LA), octadecyl acrylate and lauryl methacrylate.
According to the present invention, the polar acrylate is preferably one or a combination of two or more of hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate.
According to the invention, the mass ratio of the short-chain acrylic ester, the long-chain acrylic ester and the polar acrylic ester is 2-10:65-85:15-35.
According to the invention, the base oil is one or a combination of more than two of mineral oil, synthetic oil and vegetable oil; further preferably, the mineral oil is white oil or liquid paraffin; the synthetic oil is poly alpha olefin or polyester oil; the vegetable oil is coconut oil, soybean oil, cotton seed oil, palm oil or rapeseed oil.
According to the invention, the ratio of the mass of the base oil to the total mass of short-chain acrylate, long-chain acrylate and polar acrylate is preferably 1:7-9.
According to a preferred embodiment of the invention, the molecular weight regulator is n-dodecyl mercaptan, diisopropyl xanthogenate disulfide or sulphur; the addition mass of the molecular weight regulator is 10-20% of the total mass of short-chain acrylic ester, long-chain acrylic ester and polar acrylic ester, and more preferably 12-15%.
Preferably, according to the present invention, the initiator is an azo-type initiator or a peroxy-type initiator; further preferably, the azo initiator is Azobisisobutyronitrile (AIBN) or azobicyclohexylcarbonitrile; the peroxy compound initiator is one or more of methyl ethyl ketone peroxide, acetylacetone peroxide, dilauroyl peroxide and tert-butyl peroxyisooctanoate; the addition mass of the initiator is 0.1-1% of the total mass of short-chain acrylic ester, long-chain acrylic ester and polar acrylic ester, and is more preferably 0.3-0.5%; the initiator is added at a temperature of 70-75 ℃.
Preferably according to the invention, the temperature of the reaction is 70-90 ℃; the reaction time is 4-6h.
The polymer brush lubricant for the water-based drilling fluid is prepared by adopting the preparation method; the number average molecular weight of the polymer brush lubricant for the water-based drilling fluid is 3500-4500.
The invention also provides a water-based drilling fluid, which comprises the polymer brush lubricant for the water-based drilling fluid.
The invention has the technical characteristics and beneficial effects that:
1. according to the invention, the polyacrylate polymer brush lubricant with excellent temperature resistance and high grafting degree is prepared by using the acrylate monomer composition for polymerization, and the introduction of short-chain acrylate leads the obtained lubricant polymer to contain rigid branched chains, so that the steric hindrance of groups is increased, the temperature resistance of the copolymer can be improved, the copolymer can have higher stability at high temperature, and experiments prove that the lubricant can resist 220 ℃ high temperature; the polar acrylic ester can enhance the adsorption capacity of the copolymer on the surface of the drilling tool, and a polymer film is formed on the surface of the metal; the long chain acrylate can expand the adsorption area and provide additional lubrication film strength.
2. The lubricant disclosed by the invention has an excellent lubricating effect, a certain amount of hydroxyl groups are contained in the lubricant molecules, the hydroxyl groups can be effectively adsorbed on the surface of a drilling tool, and a wide and compact film structure is formed on the surface of the drilling tool by combining a polymer brush structure, so that friction between the drilling tool and rock is effectively reduced, and an excellent lubricating effect is achieved; meanwhile, the long-chain acrylic ester can enlarge the adsorption area and provide additional lubricating film strength. At normal temperature, 0.5% of the lubricant of the invention is added into 4% of base slurry, and the reduction rate of the lubrication coefficient is 90.6%.
3. The lubricant of the invention has good environmental protection performance and EC 50 ＞30000ppm，BOD 5 /COD Cr More than 25%, which indicates that the material is nontoxic and easy to biodegrade. Therefore, the invention is not only suitable for deep ultra-deep oil and gas drilling, but also suitable for the drilling of geothermal wells and environment sensitive areas.
Detailed Description
The invention is further illustrated, but not limited, by the following examples.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents, materials, and apparatus, unless otherwise specified, are all commercially available.
Example 1
A preparation method of a polymer brush lubricant for water-based drilling fluid comprises the following steps:
(1) 8.0g of No. 5 white oil is added into a three-neck flask provided with a rotor, a reflux condenser and a nitrogen protection device;
(2) 2.0g of methyl methacrylate, 48.0g of 2-dodecyl acrylate and 12.8g of hydroxyethyl acrylate are uniformly mixed and stirred, then dissolved in base oil, and stirred to obtain a solution;
(3) Adding 8.0g of n-dodecyl mercaptan into the prepared solution, and then bubbling with nitrogen; heating to 75 ℃ under the condition of stirring speed of 350r/min in nitrogen atmosphere; adding 0.185g of azodiisobutyronitrile into the system, and then reacting for 4 hours at 85 ℃, wherein the stirring speed is 350r/min in the reaction process; and after the reaction is finished, naturally cooling to room temperature to obtain the polymer brush lubricant for the water-based drilling fluid.
The number average molecular weight of the polymer brush lubricant for water-based drilling fluid prepared in this example was 3900.
Example 2
A preparation method of a polymer brush lubricant for water-based drilling fluid comprises the following steps:
(1) 8.0g of No. 5 white oil is added into a three-neck flask provided with a rotor, a reflux condenser and a nitrogen protection device;
(2) 3.0g of methyl methacrylate, 40.0g of 2-dodecyl acrylate and 14.0g of hydroxyethyl acrylate are uniformly mixed and stirred, then dissolved in base oil, and stirred to obtain a solution;
(3) Adding 8.0g of n-dodecyl mercaptan into the prepared solution, and then bubbling with nitrogen; heating to 75 ℃ under the condition of stirring speed of 350r/min in nitrogen atmosphere; adding 0.185g of azodiisobutyronitrile into the system, and then reacting for 4 hours at 85 ℃, wherein the stirring speed is 350r/min in the reaction process; and after the reaction is finished, naturally cooling to room temperature to obtain the polymer brush lubricant for the water-based drilling fluid.
Example 3
A preparation method of a polymer brush lubricant for water-based drilling fluid comprises the following steps:
(1) 8.0g of No. 5 white oil is added into a three-neck flask provided with a rotor, a reflux condenser and a nitrogen protection device;
(2) 2.0g of methyl methacrylate, 40.0g of 2-dodecyl acrylate and 20.0g of hydroxyethyl acrylate are uniformly mixed and stirred, then dissolved in base oil, and stirred to obtain a solution;
(3) Adding 8.0g of n-dodecyl mercaptan into the prepared solution, bubbling with nitrogen, and heating to 75 ℃ under the condition of stirring speed of 350r/min; adding 0.185g of azodiisobutyronitrile into the system, and then reacting for 4 hours at 85 ℃, wherein the stirring speed is 350r/min in the reaction process; and after the reaction is finished, naturally cooling to room temperature to obtain the polymer brush lubricant for the water-based drilling fluid.
Example 4
A method of preparing a polymer brush lubricant for water-based drilling fluids as described in example 1, except that: the azobisisobutyronitrile amount in step (3) was 0.365g.
Example 5
A method of preparing a polymer brush lubricant for water-based drilling fluids as described in example 1, except that: the amount of n-dodecyl mercaptan added in step (3) was 12.0g.
Comparative example 1
A method of preparing a lubricant for water-based drilling fluids is described in example 1, except that: in the step (3), n-dodecyl mercaptan is not added.
Comparative example 2
A method of preparing a lubricant for water-based drilling fluids is described in example 1, except that: the amount of n-dodecyl mercaptan added in step (3) was 4.0g.
Comparative example 3
A method of preparing a lubricant for water-based drilling fluids is described in example 1, except that: no methyl methacrylate is added in step (1).
Comparative example 4
A method of preparing a lubricant for water-based drilling fluids is described in example 1, except that: no hydroxyethyl acrylate is added in step (1).
Comparative example 5
A method of preparing a lubricant for water-based drilling fluids is described in example 1, except that: the amount of 2-dodecyl acrylate added in the step (1) was 20.0g.
Test examples
The lubricants prepared in the examples and comparative examples were evaluated for the following properties:
(1) Effect of Polymer brush Lubricants on drilling fluid lubrication coefficients
Preparing bentonite-based slurry: 16g of bentonite is slowly added into 400mL of distilled water while stirring, and then the mixture is aged for 24 hours at room temperature to prepare bentonite slurry with the mass and volume percentage content of 4%.
Preparing drilling fluid samples: 400mL of the base slurry was taken, 4g of the lubricant products prepared in the examples and comparative examples, respectively, were added and stirred at 3000r/min for 20min.
Performance test: according to the standard SY/T6094-94, an extreme pressure lubrication instrument is adopted to measure the lubrication coefficient of drilling fluid, and the calculation formula is as follows: f= (n1×34)/(100×n2); wherein: f is the lubrication coefficient; n1 is the lubrication reading of the drilling fluid; n2 is the lubrication reading of the clean water and 34 is the correction factor. And then calculating the reduction rate of the lubrication coefficient, wherein the formula is as follows: r= (f 0-f 1)/f0×100%; wherein: r is the reduction rate of the lubrication coefficient, f0 is the lubrication coefficient of the drilling fluid before the lubricant is added, and f1 is the lubrication coefficient of the drilling fluid after the lubricant is added. The experimental results are shown in Table 1.
TABLE 1 reduction rate of lubricating coefficient of Lubricants for drilling fluids in Bentonite-based slurry
As can be seen from Table 1, the examples added to the base slurry had little effect on the viscosity, the reduction rate of the lubricating coefficient was high, and the lubricating effect was remarkable. The effect on viscosity was slightly smaller and the lubrication effect was more pronounced compared to the comparative example. Comparing example 1, example 2, example 3 and comparative example 5, it can be seen that when the ratio of the long-chain acrylic ester is relatively high, the reduction rate of the lubrication coefficient of the sample is slightly high, the lubrication effect is better, and when the content of the long-chain acrylic ester is relatively low, the performance of the obtained lubricant is poor; as can be seen from example 4, increasing the amount of initiator did not improve the lubricating properties, indicating that the amount of initiator added had less effect on the lubricant properties; as can be seen from comparative examples 1 and 2, the absence or too small addition of the molecular weight regulator can cause the molecular weight of the polymer to be too large, so that the reactant is crosslinked and is gelatinous, and as can be seen from example 5, the addition of the molecular weight regulator is increased to cause the lubricating property of the sample to be slightly lower than that of example 1, which indicates that the addition of the molecular weight regulator is in the preferred range of the invention, and the obtained lubricant has excellent property; as can be seen from comparative examples 3 and 4, the absence of either the short-chain acrylate or the polar acrylate resulted in a significant decrease in the lubricating properties of the copolymer, indicating that three different acrylates all play a critical role in improving the lubricating properties.
(2) Evaluation results of temperature resistance of Lubricants for drilling fluids
Aging treatment of drilling fluid: the reduction rate of the lubrication coefficient of the system after 16 hours of hot rolling at 140 ℃, 180 ℃ and 220 ℃ was measured by using a roller heating furnace.
Performance test after aging: after aging, stirring for 20min at 3000r/min, and testing the reduction rate of the lubrication coefficient according to the line standard SY/T6094-94, and the experimental results are shown in Table 2.
Table 2 results of evaluation of temperature resistance of lubricants for drilling fluids
The temperature resistance test was conducted in examples 1, 3 and 4, and from the results of the test, the reduction rate of the lubrication coefficient was decreased with the increase of the temperature, but was higher than 70%. It can be seen that the example still has better lubrication performance at high temperature, and the best effect is example 1. The invention has obvious effect of resisting ultra-high temperature lubrication.
(3) Lubricating property of lubricant for drilling fluid under high density condition
High density basePreparing slurry: under stirring, 1.5g of low-viscosity carboxymethyl cellulose, 3g of high-temperature resistant modified starch and 580g of barite are added into 300mL of bentonite-based slurry, and stirring is carried out at high speed (11000 r/min) for 30min to obtain the bentonite-based slurry with the density of 2.0g/cm 3 Is used as a base stock of the (c) polymer.
400mL of the high-density base stock was taken, the lubricants prepared in examples 1 to 5 and comparative examples 2 to 3 were added to the high-density base stock, the mass/volume percentage content of the lubricants in the high-density base stock was 1% (the added lubricants were 4 g), and the density of the system and the reduction rate of the lubrication coefficient were measured, and the results are shown in Table 3.
TABLE 3 lubrication coefficient and reduction rate of lubrication coefficient of lubricants for drilling fluids in high density base slurry
As can be seen from Table 3, the examples 1-5 and comparative examples 2-3 were tested for high density with less impact on density after being added to the high density base stock, and the reduction in the coefficient of lubrication in the high density base stock was far higher than the standard of not less than 35% in the drilling fluid requirements.
(4) Lubricating property of lubricant for drilling fluid under high-salt condition
Preparing high-salt-base slurry: slowly adding 16g of bentonite into 400mL of distilled water under stirring, and aging for 24 hours at room temperature to prepare bentonite-based slurry with the mass and volume percentage content of 4%; and (3) respectively adding 5% (20 g), 15% (60 g), 25% (100 g) and 35% (140) NaCl (mass volume percentage) into 4% bentonite base slurry, and stirring to obtain base slurries with different concentrated salinity.
The lubricants (8 g) prepared in examples 1, 3 and 4 were added to the above-mentioned high-salt-content slurry, the mass volume percentage content of the lubricants in the high-salt-content slurry was 2%, and the density and the coefficient of lubrication reduction rate of the system were measured, and the results are shown in Table 4.
TABLE 4 lubrication coefficient and reduction rate of lubrication coefficient of lubricants for drilling fluids in high salt-based slurries
As can be seen from table 4, the reduction rate of the lubricating coefficient of the samples in the high-salt environment is reduced with the increase of the salt concentration, but the reduction rate of the lubricating coefficient in the high-salt slurry of 35% is still higher, which indicates that the samples have better lubricating effect in the high-salt environment.
(5) Evaluation of biotoxicity
Biotoxicity evaluation: according to the allowable value of biotoxicity of oilfield chemical agent and drilling fluid, if the biotoxicity test result is not less than 20000mg/L, the requirement of biotoxicity is met. The lubricants prepared in examples 1 to 5 were subjected to a luminous bacillus biotoxicity test, and the results are shown in table 5.
TABLE 5 biological performance test results of lubricants for drilling fluids
| Lubricant | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| EC50/ppm | 48960 | 45670 | 47820 | 41430 | 40610 |
| Toxicity grade | Nontoxic | Nontoxic | Nontoxic | Nontoxic | Nontoxic |
| BOD5/CODCr | 30.9％ | 29.8％ | 30.5％ | 26.3％ | 27.9％ |
| Degradability of | Is easy to degrade | Is easy to degrade | Is easy to degrade | Is easy to degrade | Is easy to degrade |
The EC50 of the products of each embodiment is more than 30000ppm, and BOD5/CODCr is more than 25%, which shows that the products are nontoxic, easy to biodegrade and good in environmental protection performance.
As can be seen from the above experimental results, the ultra-high temperature resistant lubricant of the invention has the remarkable advantages: firstly, the invention evaluates the effects of temperature resistance, salt resistance and high density indoors, has high-efficiency lubrication effect in different drilling fluid systems and well slurries, has good compatibility, can resist 220 ℃ ultrahigh temperature, and still has excellent lubrication effect after aging at ultrahigh temperature; secondly, the invention has the advantages of no toxicity, easy biodegradation and good environmental protection performance, and is beneficial to improving the environmental protection performance of drilling fluid and the sustainable development level of oil and gas exploration and development.
Claims (7)
1. A preparation method of a polymer brush lubricant for water-based drilling fluid comprises the following steps:
mixing and stirring short-chain acrylic ester, long-chain acrylic ester and polar acrylic ester uniformly, dissolving in base oil, and then adding a molecular weight regulator; under the nitrogen atmosphere, adding an initiator to react; naturally cooling to room temperature after the reaction is finished, and obtaining the polymer brush lubricant for the water-based drilling fluid; the number average molecular weight of the polymer brush lubricant for the water-based drilling fluid is 3500-4500;
the short-chain acrylic ester is one or the combination of more than two of methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate and propyl-2-methyl-2-acrylic ester;
the long-chain acrylic ester is one or the combination of more than two of 2-dodecyl acrylate, octadecyl acrylate and lauryl methacrylate;
the polar acrylic ester is one or the combination of more than two of hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate;
the mass ratio of the short-chain acrylic ester to the long-chain acrylic ester to the polar acrylic ester is 2-10:65-85:15-35;
the molecular weight regulator is n-dodecyl mercaptan, diisopropyl disulfide xanthate or sulfur; the added mass of the molecular weight regulator is 10-20% of the total mass of short-chain acrylic ester, long-chain acrylic ester and polar acrylic ester.
2. The method for producing a polymer brush lubricant for water-based drilling fluids according to claim 1, wherein the base oil is one or a combination of two or more of mineral oil, synthetic oil, and vegetable oil; the ratio of the mass of the base oil to the total mass of the short-chain acrylic ester, the long-chain acrylic ester and the polar acrylic ester is 1:7-9.
3. The method for preparing the polymer brush lubricant for the water-based drilling fluid according to claim 1, wherein the added mass of the molecular weight regulator is 12-15% of the total mass of the short-chain acrylic ester, the long-chain acrylic ester and the polar acrylic ester.
4. The method for preparing a polymer brush lubricant for water-based drilling fluids according to claim 1, wherein the initiator is azo-type initiator or peroxy-type initiator; the addition mass of the initiator is 0.1-1% of the total mass of the short-chain acrylic ester, the long-chain acrylic ester and the polar acrylic ester; the addition temperature of the initiator is 70-75 ℃;
the temperature of the reaction is 70-90 ℃; the reaction time is 4-6h.
5. The method for preparing a polymer brush lubricant for water-based drilling fluids according to claim 4, wherein the azo-based initiator is azobisisobutyronitrile or azobicyclohexylcarbonitrile; the peroxy compound initiator is one or more of methyl ethyl ketone peroxide, acetylacetone peroxide, dilauroyl peroxide and tert-butyl peroxyisooctanoate; the addition mass of the initiator is 0.3-0.5% of the total mass of the short-chain acrylic ester, the long-chain acrylic ester and the polar acrylic ester.
6. A polymer brush lubricant for water-based drilling fluids, which is prepared by the preparation method of claim 1.
7. A water-based drilling fluid comprising the polymer brush lubricant for a water-based drilling fluid of claim 6.
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