CN111320661A - Polyamino sulfonated alkyl glycoside, preparation method thereof and drilling fluid - Google Patents
Polyamino sulfonated alkyl glycoside, preparation method thereof and drilling fluid Download PDFInfo
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- CN111320661A CN111320661A CN201811526926.9A CN201811526926A CN111320661A CN 111320661 A CN111320661 A CN 111320661A CN 201811526926 A CN201811526926 A CN 201811526926A CN 111320661 A CN111320661 A CN 111320661A
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- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/02—Acyclic radicals, not substituted by cyclic structures
- C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
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- C07H1/00—Processes for the preparation of sugar derivatives
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- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
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- C—CHEMISTRY; METALLURGY
- 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
Abstract
The invention provides a preparation method of polyamino sulfonated alkyl glycoside, which comprises the following steps: 1) under the action of an acid catalyst, reacting alkyl glycoside, an alkylene oxide compound, an epoxy alkane chloride compound and a chlorinating agent in water to obtain a first intermediate product; 2) reacting the first intermediate product with organic amine to obtain a second intermediate product; 3) and reacting the second intermediate product with a chlorinating agent and a sulfonating agent under the action of a catalyst to obtain the polyamino sulfonated alkyl glycoside. According to the invention, functional groups such as polyether groups, sulfonated groups, amino groups and the like are introduced into the alkyl glycoside, so that the alkyl glycoside has good high-temperature resistance and strong inhibition, and is particularly suitable for high-activity shale stratum which is easy to collapse. The invention also provides the polyamino sulfonated alkyl glycoside and the drilling fluid.
Description
Technical Field
The invention belongs to the technical field of drilling fluid treating agents, and particularly relates to polyamino sulfonated alkyl glycoside, a preparation method of the polyamino sulfonated alkyl glycoside, and drilling fluid.
Background
The problem of borehole wall instability in the oil and gas drilling process is always a main factor influencing the smooth drilling construction, and particularly under the condition that deep wells, ultra-deep wells, horizontal wells and highly-deviated wells are increasingly increased, the problem is particularly prominent. According to statistics, more than 90% of borehole instability occurs in shale and shale-containing formations. The main factors influencing the stability of the well wall are physicochemical factors and mechanical factors. From the physical and chemical perspective, if the drilling fluid inhibition is insufficient, the clay minerals of the mudstone and the mud shale-containing stratum are easy to absorb water, swell and disperse in the interaction process of the water-based drilling fluid, so that the stratum strength is reduced, the stratum stress distribution is changed, and the borehole wall is unstable. The borehole wall instability is closely related to the hydration expansion dispersion effect of clay minerals, and when the drilling tool encounters a stratum which is easy to collapse such as shale, the addition of an inhibitor into the drilling fluid is one of effective ways for solving the borehole wall instability. Therefore, the development of the high-performance mud shale strong inhibitor has great significance for inhibiting the hydration, expansion and dispersion of clay minerals, effectively improving the borehole wall stabilizer, reducing the drilling cost, increasing the economic benefit and promoting safe drilling.
The drilling fluid inhibitor is mainly concentrated in polyamines, alkyl glycosides, polyalcohol, formate and the like, partially solves the problem of borehole wall instability in a drilling site, and has higher requirements on high temperature stability of each component in a drilling fluid system when drilling deep wells (more than 4572m), ultra-deep wells (more than 6000m) and formation temperature is higher (more than 200 ℃). The prior art inhibitor cannot meet the technical requirements of inhibiting and preventing collapse of high-temperature stratum.
Disclosure of Invention
In view of the above, the present invention is directed to a polyamino sulfonated alkyl glycoside, which has good high temperature resistance and strong inhibition performance.
The invention provides a preparation method of polyamino sulfonated alkyl glycoside, which comprises the following steps:
1) under the action of an acid catalyst, reacting alkyl glycoside, an alkylene oxide compound, an epoxy alkane chloride compound and a chlorinating agent in water to obtain a first intermediate product;
2) reacting the first intermediate product with organic amine to obtain a second intermediate product;
3) and reacting the second intermediate product with a chlorinating agent and a sulfonating agent under the action of a catalyst to obtain the polyamino sulfonated alkyl glycoside.
According to the invention, functional groups such as polyether group, sulfonated group, amino group and the like are introduced into the alkyl glycoside, so that the polyamino sulfonated alkyl glycoside has good high temperature resistance and strong inhibition; the method is suitable for the well drilling construction of high-activity shale with higher stratum temperature, easily collapsed stratum such as interbedded shale containing mudstone and sand shale and long horizontal section of shale gas horizontal well, avoids the complex problems in the well such as collapse and instability of well wall base pressure support and drill sticking during the well drilling, and realizes green, safe and high-speed drilling.
In the present invention, the acidic catalyst is preferably selected from hydrofluoric acid, hydrochloric acid, sulfuric acid, phosphoric acid, tartaric acid, oxalic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid or sulfamic acid.
In the present invention, the alkyl glycoside is preferably selected from methyl glycoside, ethyl glycoside, propyl glycoside, butyl glycoside, hexyl glycoside, octyl glycoside, decyl glycoside, dodecyl glycoside or tetradecyl glycoside.
The alkyl glycoside of the present invention is not particularly limited in kind and source, and may be prepared by alkyl glycoside known to those skilled in the art or by a preparation method, or may be obtained commercially, for example, the alkyl glycoside of the present invention is provided by pure petrochemical company, ltd.
In the present invention, the alkylene oxide compound is preferably selected from propylene oxide, butylene oxide or pentylene oxide.
In the present invention, the chlorooxirane is preferably selected from epichlorohydrin, chloroepoxybutane or chloroepoxypentane.
In the present invention, the chlorinating agent is preferably selected from thionyl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus oxychloride or phosphorus pentachloride.
In the present invention, the mass ratio of the epoxychloroalkane compound, the alkyl glycoside, the epoxyalkane compound, the chlorinating agent, the acidic catalyst and the water is preferably 37: (60-90): (20-40): (45-60): (4-8): (5 to 100), more preferably 37: (65-85): (25-35): (50-55): (5-7): (10-80), most preferably 37: (70-80): 30: (52-53): 6: (30-50).
In the present invention, the reaction in step 1) is preferably carried out under stirring; the stirring speed is preferably 600-1200 r/min, more preferably 700-1100 r/min, and most preferably
800 to 1000 r/min. In the invention, the reaction temperature in the step 1) is preferably 130-200 ℃, more preferably 140-190 ℃, and most preferably 150-180 ℃; the reaction time in the step 1) is preferably 0.5-3 hours, more preferably 1-2.5 hours, and most preferably 1.5-2 hours. In the present invention, the pressure of the reaction in the step 1) is preferably 5 to 15MPa, more preferably 8 to 12MPa, and most preferably 10 MPa.
In the present invention, the organic amine is preferably selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or pentaethylenehexamine.
In the present invention, the mass ratio of the epichlorohydrin compound to the organic amine is preferably 37:
(60 to 90), more preferably 37: (70-80), most preferably 37: 15.
In the invention, the reaction temperature in the step 2) is preferably 60-120 ℃, more preferably 70-110 ℃, and most preferably 80-100 ℃; the reaction in step 2) is preferably carried out at normal pressure; the reaction time in the step 2) is preferably 3-10 hours, more preferably 4-9 hours, and most preferably 5-8 hours.
In the invention, the selection type of the chlorinating agent in the step 3) is consistent with the technical scheme, and is not described again. In the present invention, the chlorinating agent in the step 1) and the chlorinating agent in the step 3) may be the same or different.
In the present invention, the sulfonating agent is preferably selected from fuming sulfuric acid, chlorosulfonic acid, sulfur trioxide, sulfamic acid or sodium bisulfite.
In the present invention, the catalyst in step 3) is preferably selected from urea, ethylurea or thiourea.
In the present invention, the mass ratio of the epoxychloroalkane compound to the chlorinating agent, sulfonating agent in step 3) and catalyst in step 3) is preferably 37: (30-50): (20-60): (5-25), more preferably 37: (35-45): (30-50): (10-20), most preferably 37: 40:40:15.
In the invention, the reaction temperature in the step 3) is preferably 66-85 ℃, more preferably 70-80 ℃, and most preferably 74-76 ℃; the reaction in step 3) is preferably carried out at normal pressure; the reaction time in the step 3) is preferably 3-10 hours, more preferably 4-9 hours, and most preferably 5-8 hours.
In the present invention, after the reaction in step 3) is completed, it is preferable that the obtained reaction product is subjected to a water removal treatment to obtain polyamino sulfonated alkyl glycoside.
The preparation method of the polyamino sulfonated alkyl glycoside 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 by using water as a solvent.
The invention provides a polyamino sulfonated alkyl glycoside, which has a structure shown in a formula I:
in the formula I, R1Selected from alkyl with 1-14 carbon atoms;
R2selected from alkyl with 1-3 carbon atoms;
R3selected from alkyl with 1-3 carbon atoms;
m is 0 to 3;
n is 0 to 3;
o is 0 to 4;
p is 1 to 3.
In the present invention, said R1Preferably methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl or tetradecyl; the R is2Preferably methyl, ethyl or propyl; the R is3Preferably methyl, ethyl or propyl; m is preferably 1-2, and n is preferably 1-2; the o is preferably 1-3, and more preferably 2; said p is preferably 2.
In the invention, the number average molecular weight of the polyamino sulfonated alkyl glycoside is preferably 435-3344, more preferably 500-3000, more preferably 1000-2500, and most preferably 1500-2000.
In the present invention, the preparation method of the polyamino sulfonated alkyl glycoside 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 the polyamino sulfonated alkyl glycoside in the technical scheme or the polyamino sulfonated alkyl glycoside prepared by the method in the technical scheme.
The components of the drilling fluid are not particularly limited, and the components of the drilling fluid, which are well known to those skilled in the art, are added with the polyamino sulfonated alkyl glycoside according to the technical scheme.
The experimental result shows that when the polyamino sulfonated alkyl glycoside aqueous solution with the mass concentration of 1% rolls for 16 hours at the temperature of 200 ℃, the once recovery rate of shale is more than 98%, and the recovery rate of relative shale is more than 99%; rolling for 16 hours at 340 ℃, wherein the primary recovery rate of the shale is more than 96 percent, and the relative recovery rate of the shale is more than 99 percent. The lubricating coefficient of the polyamino sulfonated alkyl glycoside aqueous solution with the mass concentration of 3% is less than 0.04. The polyamino sulfonated alkyl glycoside 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 polyamino sulfonated alkyl glycoside provided by the invention has no biotoxicity and is green and environment-friendly.
The polyamino sulfonated alkyl glycoside provided by the invention has good high temperature resistance and strong inhibition performance, has good lubricity and compatibility, is green and environment-friendly, can be applied to drilling fluid, improves the high temperature resistance and strong inhibition performance and the lubricity of the drilling fluid, is suitable for easy collapse of high-activity shale with higher formation temperature, mudstone, sand-mudstone interbedded layers and the like and drilling of long horizontal sections of shale gas horizontal wells, avoids borehole wall collapse instability, pressure-bearing stuck drill and other downhole complex problems during downhole drilling, 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 obtained 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 obtained in example 6 of the present invention;
FIG. 7 is an infrared spectrum of a product obtained in example 7 of the present invention;
FIG. 8 is a chart of an infrared spectrum of a product produced in example 8 of the present invention;
FIG. 9 is an infrared spectrum of a product prepared in example 9 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 present invention are all commercially available products, and the alkyl glycoside used is provided by pure petrochemical company, ltd.
Example 1
Adding 37g of epichlorohydrin, 60g of methyl glycoside, 20g of ethylene oxide, 45g of thionyl chloride, 4g of hydrofluoric acid and 50g of water into a high-pressure reaction kettle, stirring at 600r/min, and reacting at the temperature of 130 ℃ and 5MPa for 0.5 hour to obtain a first intermediate product;
adding 60g of ethylenediamine into the first intermediate product, and reacting for 3 hours at the temperature of 60 ℃ and under normal pressure to obtain a second intermediate product;
30g of thionyl chloride, 20g of oleum and 5g of urea are added into the second intermediate product, the mixture is reacted for 3 hours at 66 ℃ under normal pressure to obtain a reddish brown transparent viscous liquid, and then water is removed to obtain the polyamino sulfonated methyl glycoside, wherein the yield is 95.81%.
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: 3377cm-1Is the stretching vibration peak of an O-H bond, 2840-2980 cm-11159cm is the stretching vibration peak of C-H bond in methyl and methylene-1The peak is the stretching vibration peak of C-O-C, and the glucoside structure can be determined; 1411cm-1Is the absorption peak of the C-N bond, 1197cm-1The structure containing the amine group can be determined for the peak of the bending vibration of the C-N bond(ii) a Wave number 1173cm-1、990cm-1Is a characteristic peak of a sulfonic acid group. Indicating that the amido and the sulfonic acid groups are introduced into the molecular structure of the glucoside.
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, R1Is methyl, R2Is methyl, R3Is methyl, m is 0 to 3, n is 0 to 3, o is 0, and p is 1 to 3.
Example 2
Adding 37g of chloroepoxy butane, 65g of ethyl glucoside, 24g of epoxybutane, 50g of sulfuryl chloride, 5g of hydrochloric acid and 60g of water into a high-pressure reaction kettle, stirring at the speed of 700r/min, and reacting at the temperature of 140 ℃ for 1 hour under 6MPa to obtain a first intermediate product;
adding 70g of diethylenetriamine into the first intermediate product, and reacting for 4 hours at the temperature of 70 ℃ and under normal pressure to obtain a second intermediate product;
adding 35g of sulfuryl chloride, 25g of chlorosulfonic acid and 7g of ethyl urea into the second intermediate product, reacting for 4 hours at 70 ℃ under normal pressure to obtain a reddish brown transparent viscous liquid, and then removing water to obtain the polyamino sulfonated ethyl glycoside, wherein the yield is 95.99%.
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: 3375cm-1Is the stretching vibration peak of an O-H bond, 2840-2980 cm-11157cm is the stretching vibration peak of C-H bond in methyl and methylene-1The peak is the stretching vibration peak of C-O-C, and the glucoside structure can be determined; 1405cm-1Is the absorption peak of the C-N bond, 1194cm-1The bending vibration peak of the C-N bond can determine the structure containing the amino; wave number 1171cm-1、987cm-1Is a characteristic peak of a sulfonic acid group. Indicating that the amido and the sulfonic acid groups are introduced into the molecular structure of the glucoside.
The method provided by embodiment 2 of the invention can prepare a target product comprising a structure of formula 2:
in the formula 2, R1Is ethyl, R2Is ethyl, R3Is ethyl, m is 0 to 3, n is 0 to 3, o is 1, and p is 1 to 3.
Example 3
Adding 37g of epoxy chloropentane, 70g of propyl glucoside, 28g of epoxy pentane, 55g of phosphorus trichloride, 6g of sulfuric acid and 70g of water into a high-pressure reaction kettle, stirring at the speed of 800r/min, and reacting at the temperature of 150 ℃ for 2 hours under the pressure of 7MPa to obtain a first intermediate product;
adding 80g of triethylene tetramine into the first intermediate product, and reacting for 5 hours at the temperature of 80 ℃ and under normal pressure to obtain a second intermediate product;
adding 40g of phosphorus trichloride, 30g of sulfur trioxide and 9g of thiourea into the second intermediate product, reacting for 5 hours at 75 ℃ under normal pressure to obtain a reddish brown transparent viscous liquid, and then removing water to obtain the polyamino sulfonated propyl glycoside, wherein the yield is 96.14%.
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: 3373cm-1Is the stretching vibration peak of an O-H bond, 2840-2980 cm-11153cm is the stretching vibration peak of C-H bond in methyl and methylene-1The peak is the stretching vibration peak of C-O-C, and the glucoside structure can be determined; 1401cm-1Is the absorption peak of the C-N bond, 1192cm-1The bending vibration peak of the C-N bond can determine the structure containing the amino; wave number 1170cm-1、983cm-1Is a characteristic peak of a sulfonic acid group. Indicating that the amido and the sulfonic acid groups are introduced into the molecular structure of the glucoside.
The method provided by embodiment 3 of the invention can prepare a target product with a structure shown in formula 3:
formula 3In, R1Is propyl, R2Is propyl, R3Is propyl, m is 0 to 3, n is 0 to 3, o is 2, and p is 1 to 3.
Example 4
Adding 37g of epichlorohydrin, 80g of butyl glucoside, 32g of propylene oxide, 60g of phosphorus oxychloride, 7g of phosphoric acid and 80g of water into a high-pressure reaction kettle, stirring at 900r/min, and reacting at the temperature of 160 ℃ and 8MPa for 3 hours to obtain a first intermediate product;
adding 90g of tetraethylenepentamine into the first intermediate product, and reacting for 6 hours at the temperature of 90 ℃ and under normal pressure to obtain a second intermediate product;
and adding 50g of phosphorus oxychloride, 40g of sulfamic acid and 12g of urea into the second intermediate product, reacting for 6 hours at 85 ℃ under normal pressure to obtain a reddish-brown transparent viscous liquid, and then removing water to obtain the polyamino sulfonated butyl glucoside, wherein the yield is 96.31%.
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: 3371cm-1Is the stretching vibration peak of an O-H bond, 2840-2980 cm-11151cm is the stretching vibration peak of C-H bond in methyl and methylene-1The peak is the stretching vibration peak of C-O-C, and the glucoside structure can be determined; 1399cm-1Is absorption peak of C-N bond, 1190cm-1The bending vibration peak of the C-N bond can determine the structure containing the amino; wave number 1169cm-1、981cm-1Is a characteristic peak of a sulfonic acid group. Indicating that the amido and the sulfonic acid groups are introduced into the molecular structure of the glucoside.
The method provided by embodiment 4 of the invention can prepare a target product comprising a structure of formula 4:
in the formula 4, R1Is butyl, R2Is methyl, R3Is methyl, m is 0 to 3, n is 0 to 3, o is 3, and p is 1 to 3.
Example 5
Adding 37g of epichlorohydrin, 90g of hexyl glucoside, 36g of epoxypropane, 60g of phosphorus pentachloride, 8g of tartaric acid and 90g of water into a high-pressure reaction kettle, stirring at 1000r/min, and reacting at the temperature of 170 ℃ and 9MPa for 3 hours to obtain a first intermediate product;
adding 90g of pentaethylenehexamine into the first intermediate product, and reacting for 8 hours at the temperature of 100 ℃ and under normal pressure to obtain a second intermediate product;
and adding 50g of phosphorus pentachloride, 50g of sodium bisulfite and 16g of urea into the second intermediate product, reacting for 7 hours at 85 ℃ under normal pressure to obtain a reddish-brown transparent viscous liquid, and then removing water to obtain the polyamino sulfonated hexyl glycoside, wherein the yield is 96.44%.
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: 3369cm-1Is the stretching vibration peak of an O-H bond, 2840-2980 cm-1Is the stretching vibration peak of C-H bond in methyl and methylene, 1149cm-1The peak is the stretching vibration peak of C-O-C, and the glucoside structure can be determined; 1397cm-1Is the absorption peak of the C-N bond, 1187cm-1The bending vibration peak of the C-N bond can determine the structure containing the amino; wave number 1168cm-1、982cm-1Is a characteristic peak of a sulfonic acid group. Indicating that the amido and the sulfonic acid groups are introduced into the molecular structure of the glucoside.
The method provided by embodiment 5 of the invention can prepare a target product comprising a structure of formula 5:
in the formula 5, R1Is hexyl, R2Is methyl, R3Is methyl, m is 0 to 3, n is 0 to 3, o is 4, and p is 1 to 3.
Example 6
Adding 37g of epichlorohydrin, 90g of octyl glucoside, 40g of propylene oxide, 60g of thionyl chloride, 8g of oxalic acid and 100g of water into a high-pressure reaction kettle, stirring at 1200r/min, and reacting at the temperature of 180 ℃ and 10MPa for 3 hours to obtain a first intermediate product;
adding 90g of tetraethylenepentamine into the first intermediate product, and reacting for 9 hours at the temperature of 120 ℃ and under normal pressure to obtain a second intermediate product;
and adding 50g of thionyl chloride, 60g of sulfamic acid and 18g of urea into the second intermediate product, reacting for 8 hours at 85 ℃ under normal pressure to obtain a reddish-brown transparent viscous liquid, and then removing water to obtain polyamino sulfonated octyl glucoside, wherein the yield is 96.29%.
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: 3368cm-1Is the stretching vibration peak of an O-H bond, 2840-2980 cm-1Is the stretching vibration peak of C-H bond in methyl and methylene, 1148cm-1The peak is the stretching vibration peak of C-O-C, and the glucoside structure can be determined; 1398cm-1Is the absorption peak of the C-N bond, 1184cm-1The bending vibration peak of the C-N bond can determine the structure containing the amino; wave number 1169cm-1、987cm-1Is a characteristic peak of a sulfonic acid group. Indicating that the amido and the sulfonic acid groups are introduced into the molecular structure of the glucoside.
The method provided by embodiment 6 of the invention can prepare a target product comprising a structure of formula 6:
in the formula 6, R1Is octyl, R2Is methyl, R3Is methyl, m is 0 to 3, n is 0 to 3, o is 3, and p is 1 to 3.
Example 7
Adding 37g of epichlorohydrin, 90g of decyl glucoside, 40g of propylene oxide, 60g of thionyl chloride, 8g of p-toluenesulfonic acid and 100g of water into a high-pressure reaction kettle, stirring at 1200r/min, and reacting at the temperature of 190 ℃ under 12MPa for 3 hours to obtain a first intermediate product;
adding 90g of tetraethylenepentamine into the first intermediate product, and reacting for 10 hours at the temperature of 120 ℃ and under normal pressure to obtain a second intermediate product;
and adding 50g of thionyl chloride, 60g of sulfamic acid and 20g of urea into the second intermediate product, reacting at 85 ℃ for 9 hours under normal pressure to obtain a reddish-brown transparent viscous liquid, and then removing water to obtain the polyamino sulfonated decyl glucoside, wherein the yield is 96.77%.
The product prepared in the embodiment 7 of the invention is subjected to infrared spectrum detection, the infrared spectrum is shown in figure 7, and the detection result is as follows: 3367cm-1Is the stretching vibration peak of an O-H bond, 2840-2980 cm-1Is the stretching vibration peak of C-H bond in methyl and methylene, 1147cm-1The peak is the stretching vibration peak of C-O-C, and the glucoside structure can be determined; 1395cm-1Is the absorption peak of the C-N bond, 1185cm-1The bending vibration peak of the C-N bond can determine the structure containing the amino; wave number 1167cm-1、983cm-1Is a characteristic peak of a sulfonic acid group. Indicating that the amido and the sulfonic acid groups are introduced into the molecular structure of the glucoside.
The method provided by embodiment 7 of the invention can prepare a target product comprising a structure of formula 7:
in the formula 7, R1Is decyl, R2Is methyl, R3Is methyl, m is 0 to 3, n is 0 to 3, o is 3, and p is 1 to 3.
Example 8
Adding 37g of epichlorohydrin, 90g of dodecyl glucoside, 40g of propylene oxide, 60g of thionyl chloride, 8g of dodecylbenzene sulfonic acid and 100g of water into a high-pressure reaction kettle, stirring at 1200r/min, and reacting at 14MPa and 195 ℃ for 3 hours to obtain a first intermediate product;
adding 90g of tetraethylenepentamine into the first intermediate product, and reacting for 10 hours at the temperature of 120 ℃ and under normal pressure to obtain a second intermediate product;
and adding 50g of thionyl chloride, 60g of sulfamic acid and 23g of urea into the second intermediate product, reacting at 85 ℃ for 10 hours under normal pressure to obtain a reddish-brown transparent viscous liquid, and then removing water to obtain the polyamino sulfonated dodecyl glucoside, wherein the yield is 96.95%.
The product prepared in the embodiment 8 of the invention is subjected to infrared spectrum detection, the infrared spectrum is shown in figure 8, and the detection result is as follows: 3366cm-1Is the stretching vibration peak of an O-H bond, 2840-2980 cm-1Is the stretching vibration peak of C-H bond in methyl and methylene, 1146cm-1The peak is the stretching vibration peak of C-O-C, and the glucoside structure can be determined; 1394cm-1Is the absorption peak of the C-N bond, 1184cm-1The bending vibration peak of the C-N bond can determine the structure containing the amino; wave number 1166cm-1、982cm-1Is a characteristic peak of a sulfonic acid group. Indicating that the amido and the sulfonic acid groups are introduced into the molecular structure of the glucoside.
The method provided by embodiment 8 of the invention can prepare a target product comprising a structure of formula 8:
in the formula 8, R1Is dodecyl radical, R2Is methyl, R3Is methyl, m is 0 to 3, n is 0 to 3, o is 3, and p is 1 to 3.
Example 9
Adding 37g of epichlorohydrin, 90g of tetradecyl glucoside, 40g of epoxypropane, 60g of thionyl chloride, 8g of sulfamic acid and 100g of water into a high-pressure reaction kettle, stirring at 1200r/min, and reacting at 15MPa and 200 ℃ for 3 hours to obtain a first intermediate product;
adding 90g of tetraethylenepentamine into the first intermediate product, and reacting for 10 hours at the temperature of 120 ℃ and under normal pressure to obtain a second intermediate product;
adding 50g of thionyl chloride, 60g of sulfamic acid and 25g of urea into the second intermediate product, reacting at 85 ℃ for 10 hours under normal pressure to obtain a reddish-brown transparent viscous liquid, and then removing water to obtain the polyamino sulfonated tetradecyl glycoside, wherein the yield is 97.41%.
The product prepared in the example 9 of the invention is subjected to infrared spectrum detection, the infrared spectrum is shown in figure 9, and the detection result is as follows: 3365cm-1Is the stretching vibration peak of O-H bond, 2840～2980cm-1Is the stretching vibration peak of C-H bond in methyl and methylene, 1145cm-1The peak is the stretching vibration peak of C-O-C, and the glucoside structure can be determined; 1393cm-1Is the absorption peak of the C-N bond, 1183cm-1The bending vibration peak of the C-N bond can determine the structure containing the amino; wave number 1165cm-1、981cm-1Is a characteristic peak of a sulfonic acid group. Indicating that the amido and the sulfonic acid groups are introduced into the molecular structure of the glucoside.
The method provided by embodiment 9 of the invention can prepare a target product comprising a structure of formula 9:
in the formula 9, R1Is tetradecyl, R2Is methyl, R3Is methyl, m is 0 to 3, n is 0 to 3, o is 3, and p is 1 to 3.
Example 10
Preparing the polyamino sulfonated alkyl glycoside into 1% polyamino sulfonated alkyl glycoside aqueous solution, rolling for 16 hours at the high temperature of 200 ℃ and 340 ℃, and testing the primary recovery rate and the relative recovery rate of shale according to the following methods:
stirring the sulfonated castor oil based alkyl glycoside aqueous solution with the mass concentration of 1% at a high speed of 7000 r/min for 5min, and pouring the mixture 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 G0Placing the rock debris into an aging tank, rolling the rock debris and the sulfonated castor oil based alkyl glycoside 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 recovered rock debris and recording the mass as G1(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 marking as G2(ii) a Calculating the primary recovery rate, the secondary recovery rate and the relative recovery rate of the shale according to the following formulas:
primary recovery rate of shale1/G0×100％；
Shale secondary recovery rate G2/G0×100％；
The shale relative recovery rate is × 100% of shale secondary recovery rate/shale primary recovery rate;
respectively preparing the polyamino sulfonated alkyl glycoside prepared in the embodiments 1-9 of the invention into 1% polyamino sulfonated alkyl glycoside aqueous solution, rolling for 16 hours at 200 ℃ and 340 ℃ by adopting the test method, and testing the primary recovery rate and the relative recovery rate of shale; the results are shown in Table 1.
TABLE 1 shale recovery test results of polyamino sulfonated alkyl glycosides prepared in inventive examples 1-9
Example 11
The polyamino sulfonated alkyl glycoside prepared in the embodiments 1 to 9 of the present invention is prepared into a polyamino sulfonated alkyl glycoside aqueous solution with a mass concentration of 3%, and the extreme pressure lubrication coefficient is tested at room temperature. The test method is as follows: immersing a slide block in the instrument into a 3% polyamino sulfonated alkyl glycoside aqueous solution to be tested, adjusting the torque wrench value to be 16.95N/m, operating the instrument for 5min, and reading out a numerical value X displayed on the instrument when the slide block is immersed in the 3% polyamino sulfonated alkyl glycoside aqueous solution; 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 a 3% polyamino sulfonated alkyl glycoside aqueous solution; and Y is a numerical value displayed on the instrument when the slide block is soaked in clear water.
According to GB/T16783.1-2014, oil and gas industry drilling fluid field test part 1: the compatibility of the polyamino sulfonated alkyl glycoside prepared in examples 1 to 9 of the present invention was tested according to the standards of Water-based drilling fluids.
Biotoxicity EC of polyamino sulfonated alkyl glycoside prepared in embodiments 1-9 of the invention50The values were tested as follows: the polyamino sulfonated alkyl glycoside provided by the invention is added into sodium chloride solution with the mass concentration of 3% to be respectively prepared into 0mg.dm-3、5000mg.dm-3、10000mg.dm-3、25000mg.dm-3、50000mg.dm-3、100000mg.dm-310mL of each sample solution to be tested was allowed to stand for 60 min. 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 comparison50The value is obtained.
Preparing the polyamino sulfonated alkyl glycoside prepared in the embodiments 1-9 of the invention into a polyamino sulfonated alkyl glycoside aqueous solution with the mass concentration of 3%, and testing the lubrication coefficient according to the testing method; compatibility and biotoxicity of the EC samples were tested according to the test methods described above50The values and the detection results are shown in Table 2.
TABLE 2 detection results of lubricity, compatibility and biotoxicity of the polyamino sulfonated alkyl glycoside prepared in examples 1 to 9 of the present invention
As can be seen from the data in tables 1 and 2, the polyamino sulfonated alkyl glycoside aqueous solution with the mass concentration of 1% rolls for 16 hours at 200 ℃, the primary recovery rate of shale is more than 98%, the recovery rate of relative shale is more than 99%, the primary recovery rate of shale is more than 96% and the recovery rate of relative shale is more than 99% when the solution rolls for 16 hours at 340 ℃; the temperature resistance is better. The lubricating coefficient of the polyamino sulfonated alkyl glycoside aqueous solution with the mass concentration of 3% is less than 0.04, and the aqueous solution shows better lubricating performance. The invention provides polyamino sulfonated alkyl glycoside and a conventional methodThe water-based drilling fluid can be compounded in any proportion and has better compatibility. The invention provides a polyamino sulfonated alkyl glycoside product EC50The value is more than 640000mg/L and is far more than the emission standard of 30000mg/L, and the method has no biological toxicity and is green and environment-friendly.
From the above examples, the present invention provides a method for preparing polyamino sulfonated alkyl glycoside, comprising the following steps: 1) under the action of an acid catalyst, reacting alkyl glycoside, an alkylene oxide compound, an epoxy alkane chloride compound and a chlorinating agent in water to obtain a first intermediate product; 2) reacting the first intermediate product with organic amine to obtain a second intermediate product; 3) and reacting the second intermediate product with a chlorinating agent and a sulfonating agent under the action of a catalyst to obtain the polyamino sulfonated alkyl glycoside. According to the invention, functional groups such as polyether groups, sulfonated groups, amino groups and the like are introduced into the alkyl glycoside, so that the alkyl glycoside has good high-temperature resistance and strong inhibition, and is particularly suitable for high-activity shale stratum which is easy to collapse.
While only the preferred embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of polyamino sulfonated alkyl glycoside comprises the following steps:
1) under the action of an acid catalyst, reacting alkyl glycoside, an alkylene oxide compound, an epoxy alkane chloride compound and a chlorinating agent in water to obtain a first intermediate product;
2) reacting the first intermediate product with organic amine to obtain a second intermediate product;
3) and reacting the second intermediate product with a chlorinating agent and a sulfonating agent under the action of a catalyst to obtain the polyamino sulfonated alkyl glycoside.
2. The method according to claim 1, wherein the alkyl glycoside is selected from the group consisting of methyl glycoside, ethyl glycoside, propyl glycoside, butyl glycoside, hexyl glycoside, octyl glycoside, decyl glycoside, dodecyl glycoside, and tetradecyl glycoside.
3. The process according to claim 1, characterized in that the chlorooxirane is chosen from epichlorohydrin, chloroepoxybutane or chloroepoxypentane.
4. The process according to claim 1, wherein the acidic catalyst is selected from the group consisting of hydrofluoric acid, hydrochloric acid, sulfuric acid, phosphoric acid, tartaric acid, oxalic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid and sulfamic acid.
5. The method according to claim 1, wherein the organic amine is selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or pentaethylenehexamine.
6. The method according to claim 1, wherein the chlorinating agent in step 1) and step 3) is independently selected from sulfoxide chloride, sulfuryl chloride, phosphorus trichloride, phosphorus oxychloride or phosphorus pentachloride.
7. The process according to claim 1, characterized in that the sulfonating agent is selected from fuming sulfuric acid, chlorosulfonic acid, sulfur trioxide, sulfamic acid or sodium bisulfite.
8. The method according to claim 1, wherein the catalyst in step 3) is selected from urea, ethylurea or thiourea.
9. A polyaminosulfonated alkyl glycoside having the structure of formula I:
in the formula I, R1Selected from the group consisting of those having carbon atoms1 to 14 alkyl groups;
R2selected from alkyl with 1-3 carbon atoms;
R3selected from alkyl with 1-3 carbon atoms;
m is 0 to 3;
n is 0 to 3;
o is 0 to 4;
p is 1 to 3.
10. A drilling fluid comprising the polyaminosulfonated alkyl glycoside prepared by the method of claim 1 or the polyaminosulfonated alkyl glycoside of claim 9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113929899A (en) * | 2020-06-29 | 2022-01-14 | 中石化石油工程技术服务有限公司 | Modified alkyl glycoside high-temperature-resistant inhibitor, and preparation method and application thereof |
| CN117441736A (en) * | 2023-12-22 | 2024-01-26 | 山东科赛基农生物工程有限公司 | Compound preparation containing florasulam herbicide and agricultural coconut oil synergist |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104140454A (en) * | 2013-10-29 | 2014-11-12 | 中国石油化工股份有限公司 | Polyether amine based alkyl glycoside for drilling fluid and preparation method thereof |
| CN106432376A (en) * | 2015-08-10 | 2017-02-22 | 中石化石油工程技术服务有限公司 | Amine alkyl glycoside, preparation method and applications thereof |
| CN106432378A (en) * | 2015-08-10 | 2017-02-22 | 中石化石油工程技术服务有限公司 | Polyaminoalkyl glucoside, preparation method and application thereof |
| US20170204318A1 (en) * | 2015-08-20 | 2017-07-20 | Halliburton Energy Services, Inc. | Modified hydroxyethyl cellulosic polymers for improved well bore fluids and related uses |
-
2018
- 2018-12-13 CN CN201811526926.9A patent/CN111320661A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104140454A (en) * | 2013-10-29 | 2014-11-12 | 中国石油化工股份有限公司 | Polyether amine based alkyl glycoside for drilling fluid and preparation method thereof |
| CN106432376A (en) * | 2015-08-10 | 2017-02-22 | 中石化石油工程技术服务有限公司 | Amine alkyl glycoside, preparation method and applications thereof |
| CN106432378A (en) * | 2015-08-10 | 2017-02-22 | 中石化石油工程技术服务有限公司 | Polyaminoalkyl glucoside, preparation method and application thereof |
| US20170204318A1 (en) * | 2015-08-20 | 2017-07-20 | Halliburton Energy Services, Inc. | Modified hydroxyethyl cellulosic polymers for improved well bore fluids and related uses |
Non-Patent Citations (1)
| Title |
|---|
| 雷祖猛等: "烷基糖苷及其衍生物在钻井液中的应用研究进展", 《能源化工》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113929899A (en) * | 2020-06-29 | 2022-01-14 | 中石化石油工程技术服务有限公司 | Modified alkyl glycoside high-temperature-resistant inhibitor, and preparation method and application thereof |
| CN117441736A (en) * | 2023-12-22 | 2024-01-26 | 山东科赛基农生物工程有限公司 | Compound preparation containing florasulam herbicide and agricultural coconut oil synergist |
| CN117441736B (en) * | 2023-12-22 | 2024-03-29 | 山东科赛基农生物工程有限公司 | Compound preparation containing florasulam herbicide and agricultural coconut oil synergist |
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