CN111040743B - Comb-shaped polyurethane lubricant and water-based drilling fluid - Google Patents
Comb-shaped polyurethane lubricant and water-based drilling fluid Download PDFInfo
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- 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
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- C09K8/02—Well-drilling compositions
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Abstract
The invention discloses a comb-shaped polyurethane lubricant and a water-based drilling fluid, wherein the comb-shaped polyurethane lubricant is composed of ester-soluble comb-shaped polyurethane and lubricating oil base oil; the ester-soluble comb polyurethane consists of C6～C10The hydrophobic carbon chain on the diisocyanate and ester carbon of the linear alkyl is C11～C17The lubricating oil base oil is any one or a mixture of any two or more than two of coconut oil, soybean oil, cottonseed oil and rapeseed oil which are mixed in any proportion; the comb-shaped polyurethane lubricant has the advantages of strong extreme pressure lubricating effect of the traditional oily lubricant, long lubricating duration and good recycling stability; in addition, the comb-shaped polyurethane lubricant has good compatibility with different water-based drilling fluids, so that the water-based drilling fluid containing the comb-shaped polyurethane lubricant can be widely applied to long open hole horizontal wells and wells with complex structures.
Description
Technical Field
The invention relates to the technical field of petroleum drilling, in particular to a comb-shaped polyurethane lubricant and a water-based drilling fluid.
Background
The water-based drilling fluid still has the technical problems of frequent supporting and pressing, drill sticking and the like and insufficient water power transmission and the like in the construction process of a long horizontal section complex structure well, and the main reason is the insufficient lubricity of a lubricant in the water-based drilling fluid. Therefore, research and development on the continuous adsorbability of the water-based drilling fluid lubricant on the surface of a drilling tool and improvement of the lubricating film strength of the oil lubricant are an important part of the application of the water-based drilling fluid in a long open hole section horizontal well in the future.
The published patent application CN201711091999 adopts C10-C18 mono-organic acid and alcohol to carry out esterification reaction to synthesize the non-ionic lubricant, and utilizes hydroxyl in polyester to adsorb drilling tool film, thereby effectively avoiding the interference of ionic components in drilling fluid on lubricating performance.
Patent application CN2011101612291 is published, wherein secondary amine of fatty acid amide and terminal hydroxyl of span surfactant are used in a compounding way, so that the adsorption performance of the lubricant on the surface of the drilling tool is enhanced, and the lubricating effect is improved.
Although the two lubricants adopt nonionic lubricating active components, the mutual negative interference between the lubricants and the water-based drilling fluid is effectively avoided, and the overall operation efficiency is improved; meanwhile, hydroxyl or amino in the molecular chain is adsorbed on the surface of the drilling tool to form an adsorption anchor point of a lubricating oil film, so that the lubricating efficiency is improved. However, the two lubricants only contain a small amount of polar adsorption groups in the molecular chain and are not on the same plane, which inevitably results in less adsorption anchor points of the polar groups on the friction surface, and a strong adsorption film cannot be formed, so that the actual lubricating effect hardly meets the design requirement.
Disclosure of Invention
The invention aims to provide a comb-shaped polyurethane lubricant which can effectively improve the extreme pressure film strength of the lubricant on a friction surface and further improve the lubricating effect.
It is another object of the present invention to provide a water-based drilling fluid containing the comb-like polyurethane lubricant described above.
Therefore, the technical scheme of the invention is as follows:
a comb-shaped polyurethane lubricant is composed of ester-soluble comb-shaped polyurethane and lubricating oil base oil in a weight ratio of 1: 9-3: 7; wherein the chemical structural formula of the ester-soluble comb polyurethane is as follows:
in the formula, R1Is a carbon number of C4～C10The linear alkyl group of (1); r2Is a carbon number of C11～C17From the hydrophobic segment of a fatty acid monoglyceride; m is 6 to 10.
The long polyurethane is used as a main chain, an alkyl chain containing an ester group is used as a side chain, and a polymer structure with the main chain having a regular repeated amide group structure and the side chain capable of being fully dissolved with the vegetable oil base oil is formed; the main chain is adsorbed on the surface of the drilling tool by virtue of amide groups, and the main chain has a regular repeated amide group structure, so that a plurality of amide groups on the main chain have an adsorption superposition effect, and the adsorbability of the lubricant on the surface of the drilling tool is obviously improved; and because the fatty chain side chain has the effect of being fully miscible with the vegetable oil base oil, the vegetable oil lubricating oil film is provided with additional lubricating film strength.
Preferably, the number average molecular weight of the ester-soluble comb polyurethane is 5000-6000.
Preferably, the lubricant base oil is any one or a mixture of any two or more of coconut oil, soybean oil, cottonseed oil and rapeseed oil mixed in any proportion.
Preferably, the preparation steps of the ester-soluble comb polyurethane are as follows:
s1, weighing diisocyanate and fatty acid monoglyceride with linear alkyl according to the molar ratio of (1.5-2): 1, then adding the diisocyanate with linear alkyl into a reaction bottle, heating to 70-90 ℃, dropwise adding the fatty acid monoglyceride into the reaction bottle under the stirring condition, and continuously stirring at constant temperature for 5-10 hours to obtain non-blocked polyurethane;
wherein, the diisocyanate with linear alkyl adopts diisocyanate with the carbon number of C6-C12, and the chemical structural general formula is as follows: o ═ C ═ N- (CH)2)n-N ═ C ═ O, N ═ 4 to 10; the fatty acid monoglyceride has carbon chain with carbon number of C11～C17Alkyl groups of (a);
s2, raising the reaction temperature to 100-150 ℃, dripping excessive methanol into the reaction product obtained in the step S1, continuing stirring at constant temperature for 4-6 hours after finishing dripping, and naturally cooling to room temperature to obtain a methyl-terminated polyurethane crude product;
s3, carrying out reduced pressure rotary evaporation on the polyurethane crude product obtained in the step S2, and removing unreacted methanol to obtain the ester-soluble polyurethane product.
Preferably, the fatty acid monoglyceride is one or a mixture of two or more of coconut oil acid monoglyceride, soybean oil acid monoglyceride, cotton seed oil acid monoglyceride, and palm oil acid monoglyceride at any ratio.
A lubricant for water-based drilling fluid comprises the comb-shaped polyurethane.
Compared with the prior art, the comb-shaped polyurethane lubricant is composed of comb-shaped ester soluble polyurethane and lubricating oil base oil, the main chain amide group of the ester soluble polyurethane can form multi-anchor adsorption on a friction surface, and the side chain ester group can have good compatibility with vegetable oil base oil, so that the extreme pressure film strength of the lubricant on the friction surface is effectively improved; meanwhile, the comb-shaped ester soluble polyurethane also has a good foam inhibition effect, so that the foaming of drilling fluid caused by surface active components in a water-based drilling fluid lubricant can be effectively avoided, and the comb-shaped polyurethane lubricant has the advantages of strong extreme pressure lubrication effect of the traditional oil lubricant, long lubrication duration and good recycling stability; in addition, the comb-shaped polyurethane lubricant has good compatibility with different water-based drilling fluids, so that the water-based drilling fluid containing the comb-shaped polyurethane lubricant can be widely applied to long open hole horizontal wells and wells with complex structures, and meets higher use requirements.
Detailed Description
The present invention will be further described with reference to the following examples, which are not intended to limit the invention in any way. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are commercially available.
Example 1
The comb-shaped polyurethane lubricant is prepared by adopting the following method:
s1, 1.5mol of diisocyanate A (O ═ C ═ N- (CH) was weighed2)4-N ═ C ═ O) and 1mol of monoglycerol ester of coconut oil acid; adding diisocyanate A into a reaction bottle, heating to 70 ℃, dropwise adding the coconut oil fatty acid monoglyceride into the reaction bottle under the stirring condition, and continuously stirring at constant temperature for 10 hours to obtain non-blocked polyurethane;
s2, raising the reaction temperature to 110 ℃, dripping excessive 3mol of methanol into the reaction product obtained in the step S1, continuing stirring at constant temperature for 6 hours after the dripping is finished, and naturally cooling to room temperature to obtain a methyl-terminated polyurethane crude product;
s3, carrying out reduced pressure rotary evaporation on the polyurethane crude product obtained in the step S2, and removing unreacted methanol to obtain comb-shaped ester soluble polyurethane; the test shows that the number average molecular weight of the comb ester soluble polyurethane is 6000;
s4, stirring and mixing 100g of comb ester soluble polyurethane and 900g of cottonseed oil for 2 hours at normal temperature, and obtaining a mixture, namely the acrylate copolymer lubricant Lub-01.
Example 2
The comb-shaped polyurethane lubricant is prepared by adopting the following method:
s1, 1.6mol of diisocyanate B (O ═ C ═ N- (CH) was weighed2)6-N ═ C ═ O) and 1mol of glycerol monooleate from soybean; adding diisocyanate B into a reaction bottle, heating to 80 ℃, dropwise adding the coconut oil fatty acid monoglyceride into the reaction bottle under the stirring condition, and continuously stirring at constant temperature for 5 hours to obtain non-blocked polyurethane;
s2, raising the reaction temperature to 120 ℃, dripping excessive 2.8mol of methanol into the reaction product obtained in the step S1, continuing stirring at constant temperature for 4 hours after the dripping is finished, and naturally cooling to room temperature to obtain a methyl-terminated polyurethane crude product;
s3, carrying out reduced pressure rotary evaporation on the polyurethane crude product obtained in the step S2, and removing unreacted methanol to obtain comb-shaped ester soluble polyurethane; the comb ester soluble polyurethane was tested to have a number average molecular weight of 6000
S4, stirring and mixing 200g of comb ester soluble polyurethane and 800g of soybean oil for 2 hours at normal temperature, and obtaining a mixture, namely the acrylate copolymer lubricant Lub-02.
Example 3
The comb-shaped polyurethane lubricant is prepared by adopting the following method:
s1, weighing 1.5mol of diisocyanate C (O ═ C ═ N- (CH)2)8-N ═ C ═ O) and 1mol of rapeseed oleic acid monoglyceride; adding diisocyanate C into a reaction bottle, heating to 90 ℃, dropwise adding the coconut oil fatty acid monoglyceride into the reaction bottle under the stirring condition, and continuously stirring at constant temperature for 4 hours to obtain non-blocked polyurethane;
s2, raising the reaction temperature to 120 ℃, dripping excessive 3.8mol of methanol into the reaction product obtained in the step S1, continuing stirring at constant temperature for 5 hours after the dripping is finished, and naturally cooling to room temperature to obtain a methyl-terminated polyurethane crude product;
s3, carrying out reduced pressure rotary evaporation on the polyurethane crude product obtained in the step S2, and removing unreacted methanol to obtain comb-shaped ester soluble polyurethane; the test shows that the number average molecular weight of the comb ester soluble polyurethane is 5500;
s4, stirring and mixing 250g of comb ester soluble polyurethane and 750g of rapeseed oil for 2 hours at normal temperature, and obtaining a mixture, namely the acrylate copolymer lubricant Lub-03.
Example 4
The comb-shaped polyurethane lubricant is prepared by adopting the following method:
s1, weighing 2mol of diisocyanate D (O)＝C＝N-(CH2)10-N ═ C ═ O) and 1mol of rapeseed oleic acid monoglyceride; adding diisocyanate D into a reaction bottle, heating to 90 ℃, dropwise adding the coconut oil fatty acid monoglyceride into the reaction bottle under the stirring condition, and continuously stirring at constant temperature for 5 hours to obtain non-blocked polyurethane;
s2, raising the reaction temperature to 130 ℃, dripping excessive 4mol of methanol into the reaction product obtained in the step S1, continuing stirring at constant temperature for 5 hours after the dripping is finished, and naturally cooling to room temperature to obtain a methyl-terminated polyurethane crude product;
s3, carrying out reduced pressure rotary evaporation on the polyurethane crude product obtained in the step S2, and removing unreacted methanol to obtain comb-shaped ester soluble polyurethane; the comb ester soluble polyurethane was tested to have a number average molecular weight of 5000
S4, stirring and mixing 300g of comb ester soluble polyurethane and 700g of rapeseed oil for 2 hours at normal temperature, and obtaining a mixture, namely the acrylate copolymer lubricant Lub-04.
Comparative example 1
According to the method described in example 1, except that in step S1, the coconut oil fatty acid monoglyceride is replaced with an equimolar amount of propylene glycol, thereby synthesizing a linear ester-soluble polyurethane; then, 100g of the synthesized linear ester-soluble polyurethane and 900g of soybean oil were mixed under stirring at room temperature to obtain lubricant CL-01.
Comparative example 2
According to the method described in example 2, except that in step S1, the soybean oil fatty acid monoglyceride was replaced with an equimolar amount of propylene glycol, thereby synthesizing a linear ester-soluble polyurethane; then, 200g of the synthesized linear ester-soluble polyurethane and 800g of cottonseed oil were mixed under stirring at room temperature to obtain lubricant CL-02.
Comparative example 3
According to the method described in example 2, except that in step S1, rapeseed oil fatty acid monoglyceride was replaced with an equimolar amount of propylene glycol, thereby synthesizing a linear ester-soluble polyurethane; then, 250g of the synthesized linear ester-soluble polyurethane and 750g of soybean oil were stirred and mixed at room temperature to obtain lubricant CL-03.
Comparative example 4
According to the method described in example 3, except that in step S1, rapeseed oil fatty acid monoglyceride was replaced with an equimolar amount of propylene glycol, thereby synthesizing a linear ester-soluble polyurethane; then, 300g of the synthesized linear ester-soluble polyurethane and 700g of soybean oil were stirred and mixed at room temperature to obtain lubricant CL-04.
Comparative example 5
Commercial vegetable oil lubricant, code: KD-21C (Tianjin oil field chemical Co., Ltd.).
And (3) performance testing:
firstly, comb-shaped polyurethane lubricant products Lub-01-Lub-04 prepared in examples 1-4, lubricants CL-01-CL-04 prepared in comparative examples 1-4 and a commercially available vegetable oil lubricant are respectively added into base pulp, and performance of the lubricants in the base pulp is tested.
Preparing base slurry: adding 3 parts by weight of anhydrous sodium carbonate and 40 parts by weight of bentonite (standard calcium bentonite of middle petroleum Bohai sea drilling engineering company) into 1000 parts by weight of water while stirring, continuously stirring for 12h after adding, and sealing and standing for 16h to obtain the base slurry.
The above base slurry was mixed with a lubricant under stirring so that the content of the lubricant was 0.5 wt%.
(1) Testing density change value and apparent viscosity change value:
two 400g portions of the base slurry were taken and each 2g of the lubricant sample was added thereto, stirred at a high speed for 10min, left to stand for 1min, and the density and apparent viscosity of the base slurry and the density and apparent viscosity after sample application were measured in accordance with the specifications of GB/T16783.1.
The density change value calculation formula is as follows: Δ ρ ═ ρ1-ρ0In the formula, Δ ρ is the density change value, g/cm3；ρ1Density after sample application, g/cm3；ρ0Is the density of the base pulp in g/cm3；
The calculation formula of the apparent viscosity change value is as follows: Δ AV ═ AV-AV, where: Δ AV is the apparent viscosity increase, mPas; AV (Audio video)1The apparent viscosity after sample addition, mPas; AV (Audio video)0Is the apparent viscosity of the base slurry，mPa·s。
(2) And (3) testing the lubrication coefficient: and (3) measuring the extreme pressure lubrication coefficient of the liquid to be measured after aging for 16 hours at 150 ℃ by using a Fann212 extreme pressure lubrication instrument, and calculating the reduction rate of the lubrication coefficient.
The reduction rate of the lubrication coefficient is (extreme pressure lubrication coefficient of base slurry-extreme pressure lubrication coefficient of base slurry containing lubricant)/extreme pressure lubrication coefficient of base slurry is 100%.
(3) Fluorescence test: target light, medium and heavy oils are respectively selected to prepare crude oil standard samples, and a QFA three-dimensional fluorescence spectrometer is adopted to respectively test the fluorescence grades of the lubricants provided in the examples and the comparative examples.
The specific test results of the above items are shown in table 1 below.
Table 1:
as can be seen from Table 1, the density change value, the apparent viscosity change value and the fluorescence of the comb-shaped polyurethane lubricant products Lub-01-04 prepared in examples 1-4 to the base slurry can be controlled within an index range, and the extreme pressure lubrication reduction rate of Lub-03 and Lub-04 is obviously higher than the index value; the density change value, the apparent viscosity change value and the fluorescence of the lubricants CL-01-CL-04 prepared in the comparative examples 1-4 are controlled within the index range, but the difference between the extreme pressure lubrication reduction rate and the index value is large; the commercial vegetable oil lubricant KD-21C only focuses on extreme pressure lubrication reduction rate and fluorescence indexes, has large influence on the density and apparent viscosity change value of base slurry, and is easy to cause the performance deterioration of the drilling fluid.
Secondly, adding the comb-shaped polyurethane lubricant products Lub-01-Lub-04 prepared in the examples 1-4, the lubricants CL-01-CL-04 prepared in the comparative examples 1-4 and the commercially available vegetable oil lubricant into the drilling fluid respectively, and testing the performance of the lubricants in the drilling fluid. The drilling fluid system without lubricant was used as a blank control.
Preparing a drilling fluid system: adding 2 wt% of bentonite (satisfying GB) into 300 parts by weight of water while stirring at intervals of 10 minutes5005-2010 requirement), 2 wt% NaCO3(analytically pure), 0.5 wt% NaOH (analytically pure), 1 wt% polyanionic cellulose Pac-LV (purchased from Chongqing force macro fine chemical Co., Ltd.), 3 wt% sulfonated asphalt (purchased from Henan Xinxiang Fubang oil field chemical Co., Ltd.), 2 wt% polyalcohol BZ-YRH (purchased from Bohai sea drilling engineering Co., Ltd.), 1 wt% of the above lubricant, 7 wt% KCl (analytically pure) and 28 wt% NaCl (analytically pure), and after being uniformly stirred, the well drilling fluid is weighted by barite until the density of the well drilling fluid is 2.0g/cm3。
(1) And (3) viscosity testing: and measuring and calculating the viscosity, the dynamic shear force, the dynamic-plastic ratio and the like of the drilling fluid system before aging and after aging for 16 hours at 150 ℃ by using an electric six-speed viscometer (ZNN-D6B). Wherein: apparent viscosity AV 0.5Nφ600(ii) a Plastic viscosity PV ═ Nφ600-Nφ300(ii) a Dynamic shear force YP is 0.511 (N)φ300-PV); dynamic plastic ratio YP/PV.
(2) And (3) testing the filtration loss: measuring the filtration loss of the drilling fluid system before aging and after aging for 16 hours at 150 ℃ by adopting a six-unit API water loss instrument and a high-temperature high-pressure water loss instrument;
the specific test results of the above items are shown in table 2 below.
Table 2:
the test results in table 2 show that the comb-shaped polyurethane lubricant prepared in examples 1 to 4 has a good viscosity reduction effect, improves the rheological property of a drilling fluid system, and reduces the fluid loss of the system.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (5)
1. The comb-shaped polyurethane lubricant is characterized by comprising ester-soluble comb-shaped polyurethane and lubricating oil base oil in a weight ratio of 1: 9-3: 7; wherein the chemical structural formula of the ester-soluble comb polyurethane is as follows:
in the formula, R1Is a carbon number of C4～C10Linear alkyl radical of (2), R2Is a carbon number of C11～C17M is 6 to 10.
2. The comb-shaped polyurethane lubricant according to claim 1, wherein the lubricant base oil is any one or a mixture of any two or more of coconut oil, soybean oil, cottonseed oil and rapeseed oil mixed in any proportion.
3. The comb-like polyurethane lubricant according to claim 1, characterized in that the ester-soluble comb-like polyurethane is prepared by the steps of:
s1, weighing diisocyanate and fatty acid monoglyceride with linear alkyl according to the molar ratio of (1.5-2): 1, then adding the diisocyanate with linear alkyl into a reaction bottle, heating to 70-90 ℃, dropwise adding the fatty acid monoglyceride into the reaction bottle under the stirring condition, and continuously stirring at constant temperature for 5-10 hours to obtain non-blocked polyurethane;
s2, raising the reaction temperature to 110-130 ℃, dripping excessive methanol into the reaction product obtained in the step S1, continuing stirring at constant temperature for 4-6 hours after finishing dripping, and naturally cooling to room temperature to obtain a methyl-terminated polyurethane crude product;
s3, carrying out reduced pressure rotary evaporation on the polyurethane crude product obtained in the step S2, and removing unreacted methanol to obtain the ester-soluble polyurethane product.
4. The comb-like polyurethane lubricant according to claim 3, wherein the fatty acid monoglyceride is any one of coconut oil acid monoglyceride, soybean oil acid monoglyceride, cotton seed oil acid monoglyceride, and palm oil acid monoglyceride, or a mixture of any two or more thereof mixed in any ratio.
5. A lubricant for water-based drilling fluids comprising the comb polyurethane of any of claims 1 to 4.
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