CN111320971B - Alkyl shell oligoglycoside polyether, preparation method thereof and drilling fluid - Google Patents
Alkyl shell oligoglycoside polyether, preparation method thereof and drilling fluid Download PDFInfo
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Abstract
The invention provides a preparation method of alkyl shell oligoglycoside polyether, which comprises the following steps: 1) Reacting chitosan oligosaccharide with fatty alcohol under the action of an acid catalyst to obtain alkyl chitosan oligosaccharide glycoside; 2) And reacting the alkyl-chitosan oligoglycoside with epoxide under the action of an alkaline catalyst to obtain the alkyl-chitosan oligoglycoside polyether. According to the invention, the long-chain alkyl group and the polyether group are introduced into the molecular structure of the chitosan oligosaccharide, and the alkyl chitosan oligosaccharide polyether has good lubricating property, is suitable for drilling construction of directional wells, highly deviated wells, horizontal wells and the like, avoids the underground complex problems of pressure supporting and sticking, and the like, and realizes green, safe and efficient drilling. The invention also provides alkyl shell oligoglycoside polyether and drilling fluid.
Description
Technical Field
The invention belongs to the technical field of drilling fluid treating agents, and particularly relates to alkyl shell oligoglycoside polyether, a preparation method thereof and drilling fluid.
Background
In recent years, with more and more difficult wells such as deep wells, ultra-deep wells, long horizontal section horizontal wells, extended reach wells and the like, the requirement on lubrication and anti-sticking of drilling fluid is higher and higher. Generally, mineral oil such as crude oil, diesel oil, white oil and the like is mixed in the drilling fluid to better meet the requirement of underground lubrication and anti-sticking, but the application of mineral oil lubricants is limited along with the increasing strictness of the environmental protection requirement. Therefore, the development of green and environmentally friendly high performance lubricants is becoming a major trend.
Certain work is carried out on vegetable oil and animal oil lubricants at home and abroad, the variety of products is more, but the performance of the products cannot well meet the lubricating requirements of high-difficulty wells such as long horizontal-section horizontal wells. Therefore, the development of high performance lubricants can be a focus of research by those skilled in the art.
Disclosure of Invention
In view of the above, the present invention aims to provide an alkyl chitosan oligoglycoside polyether and a preparation method thereof, wherein the alkyl chitosan oligoglycoside polyether provided by the present invention has good lubricating property.
The invention provides a preparation method of alkyl shell oligoglycoside polyether, which comprises the following steps:
1) Under the action of an acid catalyst, reacting chitosan oligosaccharide with fatty alcohol to obtain alkyl chitosan oligoglycoside;
2) And reacting the alkyl-chitosan oligoglycoside with epoxide under the action of an alkaline catalyst to obtain the alkyl-chitosan oligoglycoside polyether.
The invention introduces long-chain alkyl group and polyether group into the molecular structure of chitosan oligosaccharide, and the alkyl chitosan oligosaccharide polyether has better lubricity; the application of the oil-gas composite material in the drilling fluid can effectively solve the underground complex problems of long horizontal section pressure supporting and drill sticking of a horizontal well in the current oil-gas exploration and development process, is beneficial to shortening the drilling period and reducing the drilling cost; the chitosan oligosaccharide derivative product and the drilling fluid technology can be further improved, the technical competitiveness of the drilling fluid is improved, and the technical progress of the drilling fluid is promoted; the application of the compound has good economic benefit and social effect on site and good popularization and application prospect.
The present invention is not particularly limited in kind and source of the chitosan oligosaccharide, and chitosan oligosaccharides well known to those skilled in the art may be used and commercially available.
In the present invention, the acidic catalyst is preferably selected from hydrochloric acid, sulfuric acid, citric acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid or sulfamic acid.
In the present invention, the fatty alcohol is preferably a fatty alcohol having 8 to 18 carbon atoms, and more preferably selected from n-octanol, n-decanol, dodecanol, tetradecanol, hexadecanol, or octadecanol.
In the present invention, the mass ratio of the chitosan oligosaccharide, the fatty alcohol and the acidic catalyst is preferably 54: (120-150): (4 to 8), more preferably 54: (130 to 140): (5 to 7), most preferably 54.
In the present invention, the reaction in step 1) is preferably carried out under stirring; the stirring speed is preferably 900 to 1200r/min, more preferably 1000 to 1100r/min, and most preferably 1050r/min. In the present invention, the reaction temperature in the step 1) is preferably 110 to 140 ℃, more preferably 115 to 135 ℃, and most preferably 120 to 130 ℃; the reaction time in said step 1) is preferably 4 to 8 hours, more preferably 5 to 7 hours, most preferably 6 hours.
In the present invention, the basic catalyst is preferably selected from sodium hydroxide, potassium hydroxide or aqueous ammonia.
In the present invention, the epoxide is preferably selected from propylene oxide, butylene oxide or pentylene oxide.
In the present invention, the mass ratio of the chitosan oligosaccharide, the epoxide and the basic catalyst is preferably 54: (90-120): (5 to 15), more preferably 54: (100 to 110): (8-12), most preferably 54.
In the present invention, the reaction in step 2) is preferably carried out under stirring; the stirring speed is preferably 900 to 1200r/min, more preferably 1000 to 1100r/min, and most preferably 1050r/min. In the present invention, the reaction temperature in the step 2) is preferably 90 to 110 ℃, more preferably 95 to 105 ℃, and most preferably 100 ℃; the reaction time in said step 2) is preferably 2 to 4 hours, more preferably 2.5 to 3.5 hours, most preferably 3 hours.
The preparation method of the alkyl chitosan oligosaccharide polyether provided by the invention has the advantages of mild reaction conditions, simple process operation and no discharge of waste water, waste gas and waste residues.
The invention provides alkyl chitosan oligosaccharide polyether, which has a structure shown in a formula I:
in the formula I, R 1 Selected from alkyl with 8 to 18 carbon atoms;
R 2 selected from alkyl with 1 to 3 carbon atoms;
m is 2 to 20;
n is 1 to 30.
In the present invention, said R 1 Preferably octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl; the R is 2 Preferably methyl, ethyl or propyl; the m is preferably 5 to 15, more preferably 8 to 12, and the n is preferably 5 to 25, more preferably 10 to 20, and most preferably 15.
In the present invention, the preparation method of the alkyl chitosan oligosaccharide is the same as that described in the above technical scheme, and is not described herein again.
The invention provides a drilling fluid, which comprises alkyl shell oligoglycoside polyether in the technical scheme or alkyl shell oligoglycoside polyether prepared by the method in the technical scheme.
The components of the drilling fluid are not particularly limited, and the alkyl shell oligoglycoside polyether can be added into the drilling fluid by adopting proper drilling fluid components according to actual conditions by a person skilled in the art.
Experimental results show that the once recovery rate of shale is more than 95% and the relative recovery rate of shale is more than 99% when the alkyl chitosan oligoglycoside polyether aqueous solution with the mass concentration of 1% is hot rolled for 16 hours at 200 ℃. The lubricating coefficient of the alkyl shell oligoglycoside polyether aqueous solution with the mass concentration of 3% is less than 0.035. The alkyl shell oligoglycoside polyether provided by the invention can be compounded with water-based drilling fluid in any proportion, and the performance of the drilling fluid is not influenced. The alkyl shell oligoglycoside polyether provided by the invention has no biotoxicity and is green and environment-friendly.
The alkyl shell oligoglycoside polyether provided by the invention has good lubricity, has good inhibitive performance and compatibility, is green and environment-friendly, can be applied to drilling fluid, is suitable for drilling construction of directional wells, highly-deviated wells, horizontal wells and the like, avoids underground complex problems such as pressure supporting and sticking, improves the drilling efficiency, reduces the drilling cost and realizes green, safe and efficient drilling.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an infrared spectrum of a product prepared in example 1 of the present invention;
FIG. 2 is an infrared spectrum of a product prepared in example 2 of the present invention;
FIG. 3 is an infrared spectrum of a product obtained in example 3 of the present invention;
FIG. 4 is an infrared spectrum of a product prepared in example 4 of the present invention;
FIG. 5 is an infrared spectrum of a product obtained in example 5 of the present invention;
FIG. 6 is an infrared spectrum of a product prepared in example 6 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other examples, which may be modified or appreciated by those of ordinary skill in the art based on the examples given herein, are intended to be within the scope of the present invention.
The raw materials used in the following examples of the invention are all commercial commodities, and the chitosan oligosaccharide used is an industrial chitosan product provided by Weifang Dongxing crustal products factory.
Example 1
Adding 54g of chitosan oligosaccharide, 120g of n-octanol and 4g of hydrochloric acid into a four-neck flask with a condensation reflux and stirring device, controlling the stirring speed to be 900r/min, reacting for 4 hours at the temperature of 110 ℃ to obtain an octyl chitosan oligoglycoside n-octanol solution, and removing unreacted n-octanol through reduced pressure distillation to obtain the octyl chitosan oligoglycoside;
90g of propylene oxide and 5g of sodium hydroxide are added into Xin Jike oligoglycoside, and the mixture is reacted for 2 hours at 90 ℃ at a stirring speed of 900r/min to obtain light yellow transparent viscous octyl chitosan oligoglycoside.
The product prepared in the embodiment 1 of the invention is subjected to infrared spectrum detection, the infrared spectrum is shown in figure 1, and the detection result is as follows: 3480cm -1 Is the stretching vibration peak of an O-H bond, 2830-2950 cm -1 Is the stretching vibration peak of C-H bond in methyl and methylene, 1689cm -1 、1280cm -1 The chitosan oligosaccharide structure can be determined as the characteristic peak of the amide group; 1164cm -1 The peak is the stretching vibration peak of C-O-C, and the polyether structure can be determined. Indicating that polyether groups have been introduced into the molecular structure of the chitosan oligosaccharide.
The method provided by the embodiment 1 of the invention can prepare the target product with the structure of the formula 1:
in the formula 1, R 1 Is octyl, R 2 Is methyl, m is 2 to 20, n is 1 to 30.
Example 2
Adding 54g of chitosan oligosaccharide, 130g of n-decanol and 5g of sulfuric acid into a four-neck flask with a condensation reflux and stirring device, controlling the stirring speed to be 1000r/min, reacting for 5 hours at the temperature of 120 ℃ to obtain a decyl chitosan oligoglycoside n-octanol solution, and removing unreacted n-decanol by reduced pressure distillation to obtain decyl chitosan oligoglycoside;
100g of butylene oxide and 7g of potassium hydroxide were added to Xin Jike oligoglycoside, and reacted at 100 ℃ for 3 hours with a stirring speed of 1000r/min to obtain decyl shell oligoglycoside polyether in the form of pale yellow, transparent and viscous substance.
The product prepared in the embodiment 2 of the invention is subjected to infrared spectrum detection, the infrared spectrum is shown in figure 2, and the detection result is as follows: 3481cm -1 Is the stretching vibration peak of an O-H bond, 2830-2950 cm -1 Is the stretching vibration peak of C-H bond in methyl and methylene, 1691cm -1 、1281cm -1 The chitosan oligosaccharide structure can be determined as the characteristic peak of the amide group; 1165cm -1 The peak of stretching vibration of C-O-C can determine that the polyether structure is contained. Indicating that polyether groups have been introduced into the molecular structure of the chitosan oligosaccharide.
The method provided by embodiment 2 of the invention can prepare a target product comprising a structure of formula 2:
in the formula 2, R 1 Is decyl, R 2 Is ethyl, m is 2 to 20, n is 1 to 30.
Example 3
Adding 54g of chitosan oligosaccharide, 140g of n-dodecyl alcohol (n-dodecyl alcohol) and 6g of citric acid into a four-mouth flask with a condensation reflux and stirring device, controlling the stirring speed to be 1100r/min, reacting for 6 hours at the temperature of 130 ℃ to obtain dodecyl chitosan oligoglycoside dodecyl alcohol solution, and removing unreacted dodecyl alcohol by reduced pressure distillation to obtain dodecyl chitosan oligoglycoside;
110g of epoxy pentane and 8g of ammonia water are added into the dodecyl chitosan oligoglycoside, and the mixture reacts for 4 hours at 110 ℃ under the stirring speed of 1100r/min, so that the dodecyl chitosan oligoglycoside polyether with light yellow, transparent and sticky properties is obtained.
The product prepared in the embodiment 3 of the invention is subjected to infrared spectrum detection, the infrared spectrum is shown in figure 3, and the detection result is as follows: 3482cm -1 Is the stretching vibration peak of an O-H bond, 2830-2950 cm -1 Is the stretching vibration peak of C-H bond in methyl and methylene, 1692cm -1 、1282cm -1 The chitosan oligosaccharide structure can be determined as the characteristic peak of the amide group; 1167cm -1 The peak of stretching vibration of C-O-C can determine that the polyether structure is contained. Indicating that polyether groups are introduced into the molecular structure of the chitosan oligosaccharide.
The method provided by embodiment 3 of the invention can prepare a target product with a structure shown in formula 3:
in formula 3, R 1 Is dodecyl radical, R 2 Is propyl, m is 2 to 20, n is 1 to 30.
Example 4
Adding 54g of chitosan oligosaccharide, 150g of n-tetradecyl alcohol (tetradecyl alcohol) and 7g of p-toluenesulfonic acid into a four-neck flask with a condensation reflux and stirring device, controlling the stirring speed at 1200r/min, reacting at 140 ℃ for 7 hours to obtain tetradecyl chitosan oligoglycoside tetradecyl alcohol solution, and removing unreacted tetradecyl alcohol by reduced pressure distillation to obtain tetradecyl chitosan oligoglycoside;
120g of propylene oxide and 10g of sodium hydroxide are added into the tetradecyl chitooligoglycoside, and the mixture reacts for 4 hours at 110 ℃ under the stirring speed of 1200r/min, so that the light yellow transparent viscous tetradecyl chitooligoglycoside polyether is obtained.
The product prepared in the embodiment 4 of the invention is subjected to infrared spectrum detection, the infrared spectrum is shown in figure 4, and the detection result is as follows: 3483cm -1 Is the stretching vibration peak of the O-H bond, 2830-2950 cm- 1 Stretching vibration of C-H bond in methyl and methylenePeak, 1693cm -1 、1283cm -1 The chitosan oligosaccharide structure can be determined as the characteristic peak of the amide group; 1168cm -1 The peak of stretching vibration of C-O-C can determine that the polyether structure is contained. Indicating that polyether groups are introduced into the molecular structure of the chitosan oligosaccharide.
The method provided by embodiment 4 of the invention can prepare a target product comprising a structure of formula 4:
in the formula 4, R 1 Is tetradecyl, R 2 Is methyl, m is 2 to 20, n is 1 to 30.
Example 5
Adding 54g of chitosan oligosaccharide, 150g of n-hexadecyl alcohol (cetyl alcohol) and 8g of dodecylbenzene sulfonic acid into a four-neck flask with a condensation reflux and stirring device, controlling the stirring speed at 1200r/min, reacting for 8 hours at the temperature of 140 ℃ to obtain hexadecyl chitosan oligoglycoside hexadecyl alcohol solution, and removing unreacted cetyl alcohol by reduced pressure distillation to obtain hexadecyl chitosan oligoglycoside;
120g of propylene oxide and 12g of sodium hydroxide are added into the hexadecyl shell oligoglycoside, and the mixture reacts for 4 hours at 110 ℃ under the stirring speed of 1200r/min to obtain the pale yellow transparent viscous hexadecyl shell oligoglycoside polyether.
The product prepared in the embodiment 5 of the invention is subjected to infrared spectrum detection, the infrared spectrum is shown in figure 5, and the detection result is as follows: 3484cm -1 Is the stretching vibration peak of an O-H bond, 2830-2950 cm -1 Is the stretching vibration peak of C-H bond in methyl and methylene, 1694cm -1 、1284cm -1 The chitosan oligosaccharide structure can be determined as the characteristic peak of the amide group; 1169cm -1 The peak is the stretching vibration peak of C-O-C, and the polyether structure can be determined. Indicating that polyether groups have been introduced into the molecular structure of the chitosan oligosaccharide.
The method provided by embodiment 5 of the invention can prepare a target product comprising a structure of formula 5:
in the formula 5, R 1 Is hexadecyl, R 2 Is methyl, m is 2 to 20, n is 1 to 30.
Example 6
Adding 54g of chitosan oligosaccharide, 150g of n-octadecyl alcohol (n-octadecyl alcohol) and 8g of sulfamic acid into a four-mouth flask with a condensation reflux and stirring device, controlling the stirring speed to be 1200r/min, reacting for 8 hours at the temperature of 140 ℃ to obtain an octadecyl chitosan oligoglycoside octadecyl alcohol solution, and removing unreacted octadecyl alcohol by reduced pressure distillation to obtain octadecyl chitosan oligoglycoside;
adding 120g of propylene oxide and 15g of sodium hydroxide into the octadecyl chitosan oligoglycoside, and reacting for 4 hours at 110 ℃ at a stirring speed of 1200r/min to obtain the light yellow transparent viscous octadecyl chitosan oligoglycoside.
The product prepared in the embodiment 6 of the invention is subjected to infrared spectrum detection, the infrared spectrum is shown in figure 6, and the detection result is as follows: 3485cm -1 Is the stretching vibration peak of an O-H bond, 2830 to 2950cm -1 Is the stretching vibration peak of C-H bond in methyl and methylene, 1696cm -1 、1286cm -1 The chitosan oligosaccharide structure can be determined as the characteristic peak of the amide group; 1169cm -1 The peak of stretching vibration of C-O-C can determine that the polyether structure is contained. Indicating that polyether groups are introduced into the molecular structure of the chitosan oligosaccharide.
The method provided by embodiment 6 of the invention can prepare a target product comprising a structure of formula 6:
in the formula 6, R 1 Is octadecyl, R 2 Is methyl, m is 2 to 20, n is 1 to 30.
Example 7
The alkyl shell oligoglycoside polyether provided by the invention is prepared into an alkyl shell oligoglycoside polyether aqueous solution with the mass concentration of 1%, the aqueous solution rolls at the high temperature of 240 ℃ for 16 hours, and the shale primary recovery rate and the shale relative recovery rate are tested according to the following methods:
stirring the alkyl shell oligoglycoside polyether aqueous solution with the mass concentration of 1% at a high speed of 7000 r/min for 5min, and pouring the solution into an aging tank for later use; drying 2.0-5.0 mm of rock debris at 103 ℃ for 4h, and cooling to room temperature; weighing G 0 G, placing the rock debris into an aging tank, rolling the rock debris and the alkyl shell oligoglycoside polyether aqueous solution with the mass concentration of 1% for 16h at a set temperature, taking out the rock debris after cooling, recovering the rock debris by using a sieve with the pore diameter of 0.42mm, drying the rock debris for 4h at 103 ℃, cooling to room temperature, weighing the mass of the recovered rock debris and recording as G 1 (ii) a Then putting the weighed recovered rock debris into clear water, rolling for 16h at a set temperature, taking out after cooling, recovering the rock debris by using a sieve with the pore diameter of 0.42mm, drying for 4h at 103 ℃, cooling to room temperature, weighing the mass of the recovered rock debris, and recording as G 2 (ii) a Calculating the primary recovery rate, the secondary recovery rate and the relative recovery rate of the shale according to the following formulas:
shale primary recovery rate = G 1 /G 0 ×100％；
Shale secondary recovery = G 2 /G 0 ×100％；
Shale relative recovery = shale secondary recovery/shale primary recovery × 100%;
the alkyl-chitosan oligoglycoside polyether prepared in the embodiments 1 to 6 of the present invention was prepared into an aqueous solution of alkyl-chitosan oligoglycoside polyether with a mass concentration of 1%. By adopting the test method, the shale rolls at 240 ℃ for 16 hours, and the primary recovery rate and the relative recovery rate of the shale are tested; the results are shown in Table 1.
TABLE 1 shale recovery test results for alkyl chitosan oligoglycoside polyethers prepared in inventive examples 1-6
| Examples | High temperature rolling condition | Shale primary recovery rate% | Relative recovery of shale,% |
| 1 | 200℃、16h | 95.37 | 99.37 |
| 2 | 200℃、16h | 95.69 | 99.43 |
| 3 | 200℃、16h | 95.54 | 99.56 |
| 4 | 200℃、16h | 96.32 | 99.48 |
| 5 | 200℃、16h | 96.98 | 99.74 |
| 6 | 200℃、16h | 96.71 | 99.87 |
Example 8
The alkyl-chitosan oligoglycoside polyethers prepared in the embodiments 1 to 6 of the present invention were respectively prepared into 3% by mass aqueous solutions of alkyl-chitosan oligoglycoside polyethers, and their extreme pressure lubrication coefficients were measured at room temperature. The test method is as follows: immersing a slide block in the instrument into a 3% alkyl shell oligoglycoside polyether aqueous solution to be tested, adjusting the value of a torque wrench to be 16.95N/m, operating the instrument for 5min, and reading out the value X displayed on the instrument when the 3% alkyl shell oligoglycoside polyether aqueous solution is immersed in the slide block; the slide block in the instrument is immersed in clear water, the value of the torque wrench is adjusted to be 16.95N/m, the instrument runs for 5min, the numerical value displayed on the instrument when the slide block is immersed in the clear water is read to be Y, and the extreme pressure lubrication coefficient calculation formula is as follows:
in the above formula: k is the extreme pressure lubrication coefficient; x is a numerical value displayed on an instrument when the slider is soaked in 3% alkyl shell oligoglycoside polyether aqueous solution; and Y is a numerical value displayed on the instrument when the slide block is soaked in clear water.
The alkyl shell oligoglycoside polyethers prepared in examples 1 to 6 of the present invention were prepared into an aqueous solution of alkyl shell oligoglycoside polyether having a mass concentration of 3%, and the extreme pressure lubrication coefficient was measured by the above-described measurement method, and the measurement results are shown in table 2.
TABLE 2 lubricating property test results of alkyl-chitosan oligoglycoside polyethers prepared in examples 1 to 6 of the present invention
| Examples | Extreme pressure lubrication coefficient | Reduction of lubricity coefficient/%) |
| Clean water | 0.340 | -- |
| 1 | 0.033 | 90.29 |
| 2 | 0.034 | 90.00 |
| 3 | 0.034 | 90.00 |
| 4 | 0.029 | 91.47 |
| 5 | 0.033 | 90.29 |
| 6 | 0.031 | 90.88 |
Example 9
According to GB/T16783.1-2014 part 1 of the field test of the oil and gas industrial drilling fluid: the compatibility of the alkyl-chitosan oligoglycoside polyethers prepared in examples 1 to 6 of the present invention was tested according to the standards of Water-based drilling fluids.
Biotoxicity EC of alkyl-shell oligoglycoside polyethers prepared in examples 1 to 6 of the present invention 50 The values were tested as follows: adding the alkyl shell oligoglycoside polyether provided by the invention into the mass concentrationAre respectively prepared into 0mg.dm in 3 percent sodium chloride solution -3 、5000mg.dm -3 、10000mg.dm -3 、25000mg.dm -3 、50000mg.dm -3 、100000mg.dm -3 10mL of each sample solution to be tested was allowed to stand for 60min. Sequentially adding 10mg of luminous bacterium T3 powder into the sample solution to be detected, fully shaking and uniformly mixing, and respectively determining the biotoxicity EC of the luminous bacterium after the luminous bacterium is contacted with the sample solution to be detected for 15min by taking sodium chloride solution with the mass concentration of 3% as comparison 50 The value is obtained.
The compatibility and biological toxicity indexes EC of the alkyl-shell oligoglycoside polyethers prepared in examples 1 to 6 of the present invention were measured by the above-mentioned test methods 50 The values and the detection results are shown in Table 3.
TABLE 3 results of testing compatibility and biotoxicity of alkyl chitosan oligoglycoside polyethers prepared in examples 1 to 6 of the present invention
| Examples | EC 50 value/mg/L | Compatibility with conventional water-based drilling fluid |
| Clean water | -- | -- |
| 1 | 678600 | Compounding at any ratio |
| 2 | 674400 | Compounding in any proportion |
| 3 | 673700 | Compounding in any proportion |
| 4 | 675100 | Compounding at any ratio |
| 5 | 676300 | Compounding in any proportion |
| 6 | 679400 | Compounding in any proportion |
As can be seen from tables 1 to 3, the alkyl shell oligoglycoside polyether aqueous solution with the mass concentration of 1% provided by the invention rolls for 16 hours at 200 ℃, the primary recovery rate of shale is more than 95%, and the relative recovery rate of shale is more than 99%; shows stronger inhibition performance. The alkyl shell oligoglycoside polyether aqueous solution with the mass concentration of 3% has the lubrication coefficient of less than 0.035, the reduction rate of the lubrication coefficient of more than or equal to 90%, and shows better lubrication performance. The alkyl shell oligoglycoside polyether provided by the invention and the conventional water-based drilling fluid can be compounded in any proportion, and has good compatibility. The invention provides amidoamine chitosan EC 50 The value is more than 670000mg/L, is far greater than the discharge standard of 30000mg/L, has no biotoxicity, and is green and environment-friendly.
From the above examples, the present invention provides a method for preparing alkyl chitosan oligoglycoside polyether, comprising the following steps: 1) Reacting chitosan oligosaccharide with fatty alcohol under the action of an acid catalyst to obtain alkyl chitosan oligosaccharide glycoside; 2) And reacting the alkyl-chitosan oligoglycoside with epoxide under the action of an alkaline catalyst to obtain the alkyl-chitosan oligoglycoside polyether. According to the invention, the long-chain alkyl group and the polyether group are introduced into the molecular structure of the chitosan oligosaccharide, and the alkyl chitosan oligosaccharide polyether has good lubricating property, is suitable for drilling construction of directional wells, highly deviated wells, horizontal wells and the like, avoids the underground complex problems of pressure supporting and sticking, and the like, and realizes green, safe and efficient drilling.
While only the preferred embodiments of the present invention have been described, it should be understood that various modifications and adaptations thereof may occur to one skilled in the art without departing from the spirit of the present invention and should be considered as within the scope of the present invention.
Claims (9)
1. An alkyl-chitosan oligoglycoside polyether having the structure of formula I:
in the formula I, R 1 Selected from alkyl with 8 to 18 carbon atoms;
R 2 selected from alkyl with 1 to 3 carbon atoms;
m is 2 to 20;
n is 1 to 30.
2. A method for preparing the alkyl shell oligoglycoside polyether of claim 1, comprising the steps of:
1) Under the action of an acid catalyst, reacting chitosan oligosaccharide with fatty alcohol to obtain alkyl chitosan oligoglycoside;
2) Under the action of an alkaline catalyst, reacting the alkyl shell oligoglycoside with an epoxide to obtain alkyl shell oligoglycoside polyether;
the acidic catalyst is selected from hydrochloric acid, sulfuric acid, citric acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid or sulfamic acid.
3. The method according to claim 2, wherein the fatty alcohol is selected from n-octanol, n-decanol, dodecanol, tetradecanol, hexadecanol or octadecanol.
4. The process according to claim 2, wherein the basic catalyst is selected from sodium hydroxide, potassium hydroxide or ammonia.
5. The process according to claim 2, characterized in that the epoxide is selected from propylene oxide, butylene oxide or pentylene oxide.
6. The method of claim 2, wherein the reaction temperature in step 1) is 110 to 140 ℃; the reaction time in the step 1) is 4 to 8 hours.
7. The method as claimed in claim 2, wherein the reaction temperature in the step 2) is 90-110 ℃; the reaction time in the step 2) is 2 to 4 hours.
8. The method according to claim 2, wherein the mass ratio of the chitosan oligosaccharide, the fatty alcohol, the acidic catalyst, the epoxide and the basic catalyst is 54: (120-150): (4-8): (90-120): (5-15).
9. A drilling fluid comprising the alkyl-chitosan oligoglycoside polyether of claim 1 or the alkyl-chitosan oligoglycoside polyether prepared by the method of claim 2.
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| CN104140525A (en) * | 2013-10-29 | 2014-11-12 | 中国石油化工股份有限公司 | Preparation method of alkyl glucoside polyether for drilling fluid |
| CN106432377A (en) * | 2015-08-10 | 2017-02-22 | 中石化石油工程技术服务有限公司 | Glucoside, preparation method and applications thereof |
| CN106699921A (en) * | 2015-08-10 | 2017-05-24 | 中石化石油工程技术服务有限公司 | Polyetheraminochitosan, and preparation method and application thereof |
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| CN104140525A (en) * | 2013-10-29 | 2014-11-12 | 中国石油化工股份有限公司 | Preparation method of alkyl glucoside polyether for drilling fluid |
| CN106432377A (en) * | 2015-08-10 | 2017-02-22 | 中石化石油工程技术服务有限公司 | Glucoside, preparation method and applications thereof |
| CN106699921A (en) * | 2015-08-10 | 2017-05-24 | 中石化石油工程技术服务有限公司 | Polyetheraminochitosan, and preparation method and application thereof |
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