A modified alkyl polyglycoside high temperature inhibitor, preparation method and application thereof

Abstract

The present invention belongs to the technical field of oilfield chemical drilling fluid treatment agents. The present invention provides a modified alkyl glycoside high temperature strong inhibitor, a preparation method and application thereof. The preparation method may include: reacting halogenated epoxide, polymerized diol and alkyl glycoside under an acidic catalyst to obtain halogenated alcohol polyether alkyl glycoside; then reacting with organic amine to obtain amino polyether alkyl glycoside; then reacting with sulfonating agent aminosulfonic acid to generate a modified alkyl glycoside high temperature strong inhibitor. The modified alkyl glycoside provided by the present invention includes an alkyl glycoside group, a hydroxyalkyl group, a polyether group, an amino group and a sulfonic acid group, and has a good inhibitory and anti-collapse effect under high temperature conditions. In addition, the modified alkyl glycoside provided by the present invention has no biological toxicity. The modified alkyl glycoside provided by the present invention can be applied to drilling fluid, and is suitable for drilling and construction of shale-prone collapse formations in deep wells and ultra-deep wells with high formation temperatures, meeting the requirements of well wall stability and green environmental protection in high-temperature formations.

Description

Technical Field

[0001] The invention belongs to the technical field of oilfield chemical drilling fluid treating agents, and in particular relates to a modified alkyl polyglycoside high temperature resistant strong inhibitor, a preparation method and application thereof. Background Art

[0002] The problem of wellbore instability during oil and gas drilling in the petroleum industry has always been the main factor affecting the smooth progress of drilling construction, especially with the increasing number of deep wells, ultra-deep wells, horizontal wells, directional wells and high-angle wells, the above problem is particularly prominent. According to statistics, more than 90% of wellbore instability occurs in shale and shale-containing formations. Studies have shown that the factors affecting wellbore stability are mainly physical and chemical factors and mechanical factors. From a physical and chemical point of view, if the drilling fluid is not sufficiently inhibited, the clay minerals in the shale and shale-containing formations are very easy to absorb water, swell and disperse during the interaction with the water-based drilling fluid, resulting in a decrease in formation strength, changes in formation stress distribution, and wellbore instability. It can be said that wellbore instability is closely related to the hydration, expansion and dispersion of clay minerals. When drilling in shale and other collapse-prone formations, adding inhibitors to the drilling fluid is one of the most effective ways to solve wellbore instability. Therefore, the development of high-performance shale strong inhibitors to inhibit the hydration, expansion and dispersion of clay minerals is of great significance to effectively improve wellbore stability, reduce drilling costs, increase economic benefits, and promote safe drilling.

[0003] With the deepening of understanding of the mechanism of wellbore stability, the research on inhibitors has become more targeted and developed rapidly in recent years. According to surveys, the research on inhibitors is mainly focused on polyamines, alkyl glycosides, polyols, formates, etc., and has also partially solved the problem of wellbore instability at the drilling site. However, when drilling deep wells (>4572m) and ultra-deep wells (>6000m), the formation temperature is high (>200℃), and the requirements for the high temperature stability of each component in the drilling fluid system are higher. The existing inhibitors cannot meet the technical requirements for inhibition and collapse prevention in high-temperature formations.

[0004] Among them, alkyl glycosides have good anti-collapse effect when used in drilling fluids, but the dosage is large, the cost is high, and the inhibition performance and temperature resistance need to be improved. In view of this situation, how to make full use of the hydroxyl active sites on the molecular structure of alkyl glycosides, chemically modify them, and prepare modified alkyl glycosides that can exert high temperature resistance and anti-collapse effect at low dosage, and use them to solve the problem of well wall instability in high temperature and easy-collapse formations, has become an urgent need for field technology. Summary of the invention

[0005] In view of this, the present application provides a modified alkyl glycoside high temperature resistant strong inhibitor, its preparation method and application. The modified alkyl glycoside provided by the present invention has good inhibitory and anti-collapse performance on high temperature and easily collapsed formations such as deep wells and ultra-deep wells.

[0006] The present invention provides a modified alkyl polyglycoside high temperature resistant strong inhibitor, comprising a group with a structure shown in the following formula:

[0007]

[0008] The groups shown in formula II, formula III, formula IV and formula V are grafted onto the structure of formula I;

[0009] Among them, R1 is C1-6 alkyl; R2 is C0-2 alkylene; R3 is C0-1 alkylene, R4 is nitrogen-containing C2-8 straight carbon chain or C0-1 alkylene; n is the degree of polymerization.

[0010] Preferably, n is not more than 800; the group represented by formula IV is a polyethylene polyamine residue.

[0011] The present invention provides a method for preparing the modified alkyl polyglycoside high temperature resistant strong inhibitor as described above, comprising the following steps:

[0012] S1, mixing an alkyl glucoside, a halogenated epoxide and a polymeric diol and reacting them to obtain a halogenated alcohol polyether alkyl glucoside;

[0013] S2, reacting the halogenated alcohol polyether alkyl glycoside with an organic amine to obtain an amino polyether alkyl glycoside;

[0014] S3, reacting the amino polyether alkyl polyglycoside with aminosulfonic acid to obtain a modified alkyl polyglycoside high temperature resistant strong inhibitor.

[0015] Preferably, the alkyl glycoside is methyl glycoside, ethyl glycoside, propyl glycoside, butyl glycoside or hexyl glycoside; and the halogenated epoxide is epichlorohydrin or epichlorohydrin.

[0016] Preferably, the polymeric diol is polyethylene glycol having a degree of polymerization not exceeding 800.

[0017] Preferably, the reaction in step S1 is carried out in the presence of a first catalyst, and the first catalyst is an acidic catalyst.

[0018] Preferably, the organic amine is ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or pentaethylenehexamine.

[0019] Preferably, the reaction in step S3 is carried out in the presence of a second catalyst, and the second catalyst is one or more of urea, ethyl urea and thiourea.

[0020] Preferably, the reaction temperature in step S3 is 40-60° C., and the reaction time is more than 30 minutes.

[0021] The present invention provides the use of the modified alkyl polyglycoside high temperature resistant strong inhibitor as described above in the preparation of drilling fluid.

[0022] In the present application, the modified alkyl glycoside is modified, and the prepared modified alkyl glycoside includes the groups shown in Formula I to Formula V, that is, the modified alkyl glycoside contains structures such as alkyl glycoside groups, hydroxyalkyl groups, polyether groups, amino groups and sulfonic acid groups. The modified alkyl glycoside of the present invention is an excellent high-temperature resistant strong inhibitor product. The product is used in drilling fluids and has high inhibition and anti-collapse performance for high-temperature and easily collapsed formations such as deep wells and ultra-deep wells, which is conducive to field applications.

[0023] In addition, the present invention can use alkyl glycoside, halogenated epoxide, polymeric diol, organic amine and aminosulfonic acid as raw materials to prepare modified alkyl glycoside high temperature strong inhibitor through catalytic reaction. In the production process of the present invention, the reaction conditions are mild, the process operation is simple, there is no waste water, waste gas and waste residue discharge, and the synthesized product is green and environmentally friendly. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is the infrared detection spectrum of the product obtained in Example 1 of the present application. DETAILED DESCRIPTION

[0025] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other examples improved or modified by ordinary technicians in this field belong to the scope of protection of the present invention.

[0026] The present invention provides a modified alkyl polyglycoside high temperature resistant strong inhibitor, comprising a group with a structure shown in the following formula:

[0027]

[0028] The groups shown in formula II, formula III, formula IV and formula V are grafted onto the structure of formula I;

[0029] Among them, R1 is C1-6 alkyl; R2 is C0-2 alkylene; R3 is C0-1 alkylene, R4 is nitrogen-containing C2-8 straight carbon chain or C0-1 alkylene; n is the degree of polymerization.

[0030] The modified alkyl polyglycoside product provided by the present invention is an excellent high temperature resistant strong inhibitor, has a good inhibitory and anti-collapse effect under high temperature conditions, and has no biological toxicity. The modified alkyl polyglycoside provided by the present invention can be applied to drilling fluids, and is suitable for drilling construction in deep wells and ultra-deep wells with shale prone to collapse formations with high formation temperatures, meeting the requirements of well wall stability and green environmental protection in high temperature formations.

[0031] The modified alkyl glycoside of the present invention includes an alkyl glycoside group shown in formula I. The cyclic group structure contains a single bond that is not connected to an atom or group, which is represented by a connection bond after the reaction of the active position of the hydroxyl group of the alkyl glycoside, and is not limited to a specific position and number. In formula I, R1 is an alkyl group, specifically a C1-6 alkyl group; the C1-6 alkyl group is an alkyl group selected from 1 to 6 carbon atoms, usually a straight chain alkyl group, such as methyl (CH3), ethyl (C2H5), propyl (C3H7), butyl (C4H9), hexyl (C6H 13 ).

[0032] The modified alkyl glycoside product contains a glycoside structure as determined by infrared detection in the embodiment of the present invention; for example, at 3380 cm -1 The stretching vibration peak of the OH bond is 2830-2950cm -1 It is the stretching vibration peak of the CH bond in the methyl group.

[0033] The modified alkyl glycoside includes a hydroxyalkyl group as shown in formula II, which is an intermediate group with single bonds at both ends; and R2 is a C0-2 alkylene group. The number of carbon atoms in R2 is zero (C0), indicating that the carbon atom with a hydroxyl group is directly connected to other atoms or groups; R2 can also be a C1-2 alkylene group, that is, a methylene group (CH2) or an ethylene group (C2H4).

[0034] The modified alkyl polyglycoside includes a polyether group shown in formula III, which contains an ether bond and is an intermediate group with single bonds at both ends. In formula III, n represents the degree of polymerization, and R3 is a C0-1 alkylene group. The number of carbon atoms in R3 is zero (C0), that is, the structure of formula III is a polyoxyethylene ether group or a polyethylene glycol residue; the preferred structure of formula III in the present invention is -(O-CH2-CH2) n -O-. In addition, R3 can also be a C1 alkylene (methylene). The polymerization degree n is generally not more than 800, and is preferably any integer between 150 and 800, such as 200 / 400 / 600 / 800, etc.

[0035] In some embodiments of the present application, the infrared detection results of the modified alkyl polyglycoside product include: 1151cm -1 is the stretching vibration peak of COC, 1050~1100cm -1 It is the stretching vibration peak of the CO bond in the hydroxyl group, which can be determined to contain a polyether structure.

[0036] In addition, the modified alkyl glycoside of the present invention also includes an intermediate group shown in formula IV. Both ends of the structure of formula IV are CH2-NH-, wherein R4 is a nitrogen-containing C2-8 straight carbon chain or a C0-1 alkylene group. In some embodiments, R4 is a nitrogen-containing straight carbon chain with 2 to 8 carbon atoms, and preferably the group shown in formula IV is a polyethylene polyamine residue, such as a diethylenetriamine residue, a triethylenetetramine residue, a tetraethylenepentamine residue or a pentaethylenehexamine residue. In other embodiments, R4 is a C0-1 alkylene residue, and preferably the structure of formula IV is an ethylenediamine residue, that is, a structure with zero carbon atoms: -NH-CH2-CH2-NH-.

[0037] The modified alkyl polyglycoside product of the present application was determined by infrared detection to contain an amine structure; for example, 1419 cm -1 is the absorption peak of CN bond, 3380cm -1 is the absorption peak of NH.

[0038] In the present invention, the modified alkyl polyglycoside includes a sulfonic acid terminal group (-SO3-NH2) as shown in Formula V, which further improves the temperature resistance of the product. Infrared detection results show that 1190cm -1 、1068cm -1 、620cm -1 、530cm -1 It is the main characteristic peak of sulfonic acid group. The product is confirmed to contain sulfonic acid group.

[0039] The groups shown in formula II, formula III, formula IV and formula V are grafted on the structure of formula I; the present application has no special restrictions on the specific connection positions of the above groups and the proportions of each group, as long as an inhibitor product with stable structural performance can be obtained, for example, a reddish-brown, viscous modified alkyl glycoside product. The modified alkyl glycoside mentioned above in the present application can be applied to drilling fluids, and has good inhibition and anti-collapse performance under high temperature conditions, and can be called modified alkyl glycoside high temperature strong inhibitor, modified alkyl glycoside for drilling fluid, modified alkyl glycoside high temperature strong inhibitor for drilling fluid, modified alkyl glycoside inhibitor, etc.

[0040] In some embodiments of the present application, the modified alkyl polyglycoside high temperature resistant strong inhibitor for drilling fluid has a structure shown in Formula A:

[0041]

[0042] In formula A, the subscripts m, o, and p represent the degree of polymerization of the respective groups. For example, m is 1 to 3, o is 1 to 3, and p is 0 to 4 (including the endpoints); the molar number of the polyethylene glycol residue may be 5 to 20. In addition, R1 is an alkyl group having 1 to 6 carbon atoms; and R2 is CH2 or C2H4.

[0043] The present invention can use raw materials containing hydroxyalkyl, polyether group, amino group and sulfonic acid group to modify alkyl polyglycoside to obtain the modified alkyl polyglycoside product. Among them, the embodiment of the present invention provides a method for preparing the modified alkyl polyglycoside high temperature strong inhibitor as described above, comprising the following steps:

[0044] S1, mixing an alkyl glucoside, a halogenated epoxide and a polymeric diol and reacting them to obtain a halogenated alcohol polyether alkyl glucoside;

[0045] S2, reacting the halogenated alcohol polyether alkyl glycoside with an organic amine to obtain an amino polyether alkyl glycoside;

[0046] S3, reacting the amino polyether alkyl polyglycoside with aminosulfonic acid to obtain a modified alkyl polyglycoside high temperature resistant strong inhibitor.

[0047] In the embodiment of the present invention, alkyl glucoside, halogenated epoxide and polymeric diol are first reacted under the catalysis of an acidic catalyst to obtain halogenated alcohol polyether alkyl glucoside; and then reacted with an organic amine to obtain amino polyether alkyl glucoside.

[0048] Wherein, the carbon number of the alkyl group of the glycoside used in the present invention is ≤6, that is, the alkyl glycoside is preferably methyl glycoside, ethyl glycoside, propyl glycoside, butyl glycoside or hexyl glycoside; the halogenated epoxide is preferably epichlorohydrin or epichlorohydrin. The polymeric diol is preferably polyethylene glycol, more preferably polyethylene glycol with a degree of polymerization not exceeding 800, for example, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600 or polyethylene glycol 800. The reaction to obtain the halogenated alcohol polyether alkyl glycoside is preferably carried out in the presence of an acidic catalyst and under stirring conditions; the acidic catalyst can be recorded as the first catalyst for easy distinction from the subsequent step. The acidic catalyst can be an inorganic acid or an organic acid, and is further preferably sulfuric acid, citric acid, p-toluenesulfonic acid or dodecylbenzenesulfonic acid.

[0049] Specifically, the embodiment of the present invention can add halogenated epoxide, polyethylene glycol, alkyl glycoside, and acidic catalyst into the reactor according to the ratio of mass parts of 38: (80-320): (70-100): (4-10), control the stirring speed at 800-1200r / min, preferably react at 95-115°C for 1.0-3.0h, and reduce to 40°C to obtain a reaction solution containing chlorohydrin polyether alkyl glycoside. In the embodiment of the present invention, 70-90 parts by mass of organic amine can be slowly added to the above reaction solution, and the organic amine is preferably ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or pentaethylenehexamine; and preferably keep the temperature at 85-90°C, react for 2.0-4.0h, and obtain a reaction solution containing amino polyether alkyl glycoside.

[0050] Finally, in the embodiment of the present invention, the obtained amino polyether alkyl polyglycoside is reacted with the sulfonating agent aminosulfonic acid to generate a modified alkyl polyglycoside high temperature resistant strong inhibitor. The reaction is preferably carried out in the presence of a second catalyst, and the second catalyst (neutral catalyst) is preferably one or more of urea, ethyl urea and thiourea.

[0051] In the embodiment of the present invention, 24 to 32 parts by mass of a second catalyst and 38 to 48 parts by mass of aminosulfonic acid can be added to the reaction solution of the above-mentioned amino polyether alkyl polyglycoside, preferably reacted at 40 to 60° C. for 0.5 to 2.0 hours, and then cooled to room temperature to obtain a reddish-brown viscous modified alkyl polyglycoside high temperature resistant strong inhibitor.

[0052] Among them, the aminosulfonic acid structure is HO-SO2-NH2, which can provide sulfonic acid groups, which is beneficial to improve the temperature resistance of the product. The obtained modified alkyl polyglycoside high temperature strong inhibitor has the structure described above, that is, it contains alkyl polyglycoside groups, hydroxyalkyl groups, polyether groups, amino groups, sulfonic acid groups, etc.

[0053] The modified alkyl polyglycoside prepared by the present invention has good anti-collapse performance for high-temperature collapse-prone formations such as deep wells and ultra-deep wells, is green and environmentally friendly, has no biological toxicity, and can be applied to drilling fluids, especially for drilling construction of shale collapse-prone formations in deep wells and ultra-deep wells with high formation temperatures. In the production process of the present invention, the reaction conditions are mild, the process operation is simple, and there is no discharge of wastewater, waste gas, and waste residue, which is beneficial to environmental protection.

[0054] The present invention also provides the use of the modified alkyl polyglycoside high temperature strong inhibitor as described above in the preparation of drilling fluid. The present invention has no special restrictions on other components of the drilling fluid, and the additives commonly used in the art can be used. The amount of the modified alkyl polyglycoside added is 0.2% to 10.0%; when it is 0.2% to 1.0%, it can play a high temperature resistance and anti-collapse effect, and can solve the problem of well wall instability in high temperature prone to collapse formations.

[0055] In order to further understand the present invention, the modified alkyl polyglycoside high temperature resistant strong inhibitor provided by the present application, its preparation method and application are specifically described below in combination with the examples. However, it should be understood that these examples are implemented on the premise of the technical solution of the present invention, and detailed implementation methods and specific operation processes are given only to further illustrate the features and advantages of the present invention, rather than to limit the claims of the present invention, and the protection scope of the present invention is not limited to the following examples.

[0056] In the following examples, the yield is calculated as follows: actual product mass / theoretical product mass×100%.

[0057] Example 1

[0058] 38g of epichlorohydrin, 80g of polyethylene glycol 200, 70g of methyl glycoside and 4g of sulfuric acid were added to the reactor, and the reaction was carried out at 95°C for 1.0h at a stirring speed of 800r / min, and then the temperature was lowered to 40°C to obtain chloroalcohol polyether methyl glycoside; 70g of ethylenediamine was slowly added to the above reaction solution, and the temperature was kept at 85°C for 2.0h to obtain amino polyether methyl glycoside; 24g of urea and 38g of aminosulfonic acid were added to the reaction solution, and the reaction was carried out at 40°C for 0.5h, and then the temperature was lowered to room temperature to obtain a reddish brown viscous modified methyl glycoside high temperature strong inhibitor. The product yield was 85.66%.

[0059] The modified methyl glycoside prepared in Example 1 of the present invention was subjected to infrared detection, and the results were as follows: Figure 1 As shown. Among them, at 3380cm -1 The stretching vibration peak of the OH bond is 2830-2950cm -1 The peak of stretching vibration of CH bond in methyl group indicates the presence of glycoside structure; 1151cm -1 is the stretching vibration peak of COC, 1050~1100cm -1 The peak of stretching vibration of CO bond in hydroxyl group can be confirmed to contain polyether structure; 1419cm -1 is the absorption peak of CN bond, 3380cm -1 The absorption peak of NH can be used to determine the structure containing amine; 1190cm -1 、1068cm -1 、620cm -1 、530cm -1 It is the main characteristic peak of sulfonic acid group, confirming that it contains sulfonic acid group.

[0060] The structure of the modified alkyl glycoside prepared in Example 1 of the present invention can be seen in Formula A, wherein m is 1 to 3; o is 1 to 3; p is 0; the molar number of the polyethylene glycol residue is 5 to 20; R1 is CH3; and R2 is CH2.

[0061] Example 2

[0062] 38g of epichlorohydrin, 160g of polyethylene glycol 400, 80g of ethyl glycoside and 5g of citric acid were added to the reactor, and the reaction temperature was 100℃ for 1.5h at a stirring speed of 900r / min, and then the temperature was lowered to 40℃ to obtain chloroalcohol polyether ethyl glycoside; 80g of diethylenetriamine was slowly added to the above reaction solution, and the temperature was kept at 90℃ for 3.0h to obtain amino polyether ethyl glycoside; 28g of ethyl urea and 42g of aminosulfonic acid were added to the reaction solution, and the reaction temperature was 50℃ for 1.0h, and the temperature was lowered to room temperature to obtain a reddish brown viscous modified ethyl glycoside high temperature strong inhibitor. The product yield was 86.58%.

[0063] The modified ethyl glycoside prepared in Example 2 of the present invention was subjected to infrared detection, and the results included: -1 The stretching vibration peak of OH bond is 2831~2952cm -1 1152cm is the stretching vibration peak of the CH bond in the methyl and methylene groups, which can be used to determine the presence of glycoside structure; -1 is the stretching vibration peak of COC, 1051~1102cm -1 The peak of stretching vibration of CO bond in hydroxyl group can be confirmed to contain polyether structure; 1418cm -1 is the absorption peak of CN bond, 3381cm -1 The absorption peak of NH can be used to determine the structure containing amine; 1191cm -1 、1067cm -1 、621cm -1 、531cm -1 It is the main characteristic peak of sulfonic acid group, confirming that it contains sulfonic acid group.

[0064] The structure of the modified alkyl glycoside prepared in Example 2 of the present invention can be seen in Formula A, wherein m is 1 to 3; o is 1 to 3; p is 1; the molar number of the polyethylene glycol residue is 5 to 20; R1 is C2H5; and R2 is C2H4.

[0065] Example 3

[0066] 38g of epichlorohydrin, 240g of polyethylene glycol 600, 90g of propyl glycoside and 6g of p-toluenesulfonic acid were added to a reactor, and the reaction temperature was 105°C for 2.0h at a stirring speed of 1000r / min, and then the temperature was lowered to 40°C to obtain chloroalcohol polyether propyl glycoside; 90g of triethylenetetramine was slowly added to the above reaction solution, and the temperature was kept at 90°C for 4.0h to obtain aminopolyether propyl glycoside; 32g of thiourea and 44g of aminosulfonic acid were added to the reaction solution, and the reaction temperature was 60°C for 1.5h, and the temperature was lowered to room temperature to obtain a reddish brown viscous modified propyl glycoside high temperature strong inhibitor. The product yield was 85.37%.

[0067] The modified propyl glycoside prepared in Example 3 of the present invention was subjected to infrared detection, and the results included: -1 The stretching vibration peak of OH bond is 2832~2954cm -1 1153cm is the stretching vibration peak of the CH bond in the methyl and methylene groups, which can be used to determine the presence of a glycoside structure; -1 is the stretching vibration peak of COC, 1053~1104cm -1 1419cm is the stretching vibration peak of the CO bond in the hydroxyl group, which can be determined to contain a polyether structure; -1 is the absorption peak of CN bond, 3383cm -1The absorption peak of NH can be used to determine the structure containing amine; 1192cm -1 、1068cm -1 、622cm -1 、532cm -1 It is the main characteristic peak of sulfonic acid group, confirming that it contains sulfonic acid group.

[0068] The structure of the modified alkyl glycoside prepared in Example 3 of the present invention can be seen in Formula A, wherein m is 1 to 3; o is 1 to 3; p is 2; the molar number of the polyethylene glycol residue is 5 to 20; R1 is C3H7; and R2 is CH2.

[0069] Example 4

[0070] 38g of epichlorohydrin, 280g of polyethylene glycol 800, 100g of butyl glycoside and 7g of dodecylbenzene sulfonic acid were added to the reactor, and the reaction was carried out at 110°C for 2.5h at a stirring speed of 1100r / min, and then the temperature was lowered to 40°C to obtain chloroalcohol polyether butyl glycoside; 90g of tetraethylenepentamine was slowly added to the above reaction solution, and the temperature was kept at 90°C for 4.0h to obtain amino polyether butyl glycoside; 32g of thiourea and 48g of aminosulfonic acid were added to the above reaction solution, and the reaction was carried out at 60°C for 2.0h, and then the temperature was lowered to room temperature to obtain a reddish brown viscous modified butyl glycoside high temperature strong inhibitor. The product yield was 85.92%.

[0071] The modified butyl glycoside prepared in Example 4 of the present invention was subjected to infrared detection, and the results included: 1 The stretching vibration peak of OH bond is 2834~2955cm -1 1154cm is the stretching vibration peak of the CH bond in the methyl and methylene groups, which can be used to determine the presence of a glycoside structure; -1 is the stretching vibration peak of COC, 1054~1105cm -1 The peak of the stretching vibration of the CO bond in the hydroxyl group can be used to determine the presence of a polyether structure; 1420 cm -1 is the absorption peak of CN bond, 3384cm -1 The absorption peak of NH can be used to determine the structure containing amine; 1193cm -1 、1069cm -1 、623cm -1 、533cm -1 It is the main characteristic peak of sulfonic acid group, confirming that it contains sulfonic acid group.

[0072] The structure of the modified alkyl glycoside prepared in Example 4 of the present invention can be seen in Formula A, wherein m is 1 to 3; o is 1 to 3; p is 3; the molar number of the polyethylene glycol residue is 5 to 20; R1 is C4H9; and R2 is CH2.

[0073] Example 5

[0074] 38g of epichlorohydrin, 320g of polyethylene glycol 400, 100g of hexyl glycoside and 8g of p-toluenesulfonic acid were added to the reactor, and the reaction was carried out at 115°C for 3.0h at a stirring speed of 1200r / min, and then the temperature was lowered to 40°C to obtain chloroalcohol polyether hexyl glycoside; 90g of pentaethylenehexamine was slowly added to the above reaction solution, and the temperature was kept at 90°C for 4.0h to obtain amino polyether hexyl glycoside; 32g of urea and 48g of aminosulfonic acid were added to the reaction solution, and the reaction was carried out at 60°C for 2.0h, and then the temperature was lowered to room temperature to obtain a reddish brown viscous modified hexyl glycoside high temperature resistant strong inhibitor. The product yield was 86.96%.

[0075] The modified hexyl glycoside prepared in Example 5 of the present invention was subjected to infrared detection, and the results included: -1 The stretching vibration peak of OH bond is 2835~2956cm -1 1155cm is the stretching vibration peak of the CH bond in the methyl and methylene groups, which can be used to determine the presence of glycoside structure; -1 is the stretching vibration peak of COC, 1055~1106cm -1 The peak of stretching vibration of CO bond in hydroxyl group can be used to confirm the presence of polyether structure; 1421cm -1 is the absorption peak of CN bond, 3385cm -1 The absorption peak of NH can be used to determine the structure containing amine; 1194cm -1 、1069cm -1 、624cm -1 、534cm -1 It is the main characteristic peak of sulfonic acid group, confirming that it contains sulfonic acid group.

[0076] The structure of the modified alkyl glycoside prepared in Example 5 of the present invention can be seen in Formula A, wherein m is 1 to 3; o is 1 to 3; p is 4; the number of moles of polyethylene glycol residue is 5 to 20; R1 is C6H 13 ; R2 is CH2.

[0077] Comparative Example 1

[0078] 38g of epichlorohydrin, 80g of polyethylene glycol 200, 70g of methyl glycoside and 4g of sulfuric acid were added into a reactor, and the mixture was reacted at 95°C for 1.0h under a stirring speed of 800r / min, and then cooled to 40°C to obtain chloroalcohol polyether methyl glycoside; 70g of ethylenediamine was slowly added into the above reaction solution, and the temperature was maintained at 85°C for 2.0h to obtain amino polyether methyl glycoside.

[0079] Comparative Example 2

[0080] 38g of epichlorohydrin, 80g of polyethylene glycol 200, 70g of methyl glycoside and 4g of sulfuric acid were added into a reactor, reacted at 95°C for 1.0h under a stirring speed of 800r / min, and then cooled to 40°C to obtain chloroalcohol polyether methyl glycoside; 24g of urea and 38g of aminosulfonic acid were added to the above reaction solution, reacted at 40°C for 0.5h, and then cooled to room temperature to obtain a light yellow viscous sulfonated polyether alkyl glycoside.

[0081] Example 6

[0082] The modified alkyl glycoside product samples prepared in Examples 1-5 of the present invention and Comparative Examples 1-2 were respectively taken and heated at 240°C for 16 hours to test the relative inhibition rate of the product samples with a mass concentration of 0.7% on calcium soil and the biological toxicity EC 50 The test results are shown in Table 1.

[0083] The relative inhibition rate evaluation method of modified alkyl polyglycoside products on calcium soil is as follows: take 350mL of distilled water, add 0.5% sodium carbonate, add 10% calcium bentonite after dissolving, stir at high speed for 20min, roll at 240℃ for 16h, cool down and take out, stir at high speed for 5min, and use a six-speed rotation viscometer to measure the 100r / min reading of the drilling fluid as (Φ 100 )0; Take 350mL of distilled water, add 0.5% sodium carbonate and different contents of modified alkyl glycoside product samples, add 10% calcium bentonite after fully dissolving, stir at high speed for 20min, roll at 240℃ for 16h, cool down and take out, stir at high speed for 5min, and use a six-speed rotation viscometer to measure the 100r / min reading of the drilling fluid as (Φ 100 )1. Relative inhibition rate = ((Φ 100 )0—(Φ 100 )1) / (Φ 100 )0×100%.

[0084] The biotoxicity test method for the modified alkyl glycoside product samples is the luminescent bacteria method, and the test method is as follows: (1) First, the sample is prepared into 50000mg.dm with 3% sodium chloride solution. -3 200 mL of solution was stirred at 12000 r / min for 30 min to fully dissolve the sample. This solution was used to prepare 0 mg.dm -3 、5000mg.dm -3 、10000mg.dm -3 , 25000mg.dm -3 、50000mg.dm -3(2) Add 10 mg of luminescent bacteria T3 powder to the diluted solutions and shake thoroughly to mix. Then, use 3% sodium chloride solution as a reference to measure the relative luminescence value EC after the luminescent bacteria and the sample have been in contact for 15 minutes. 50 The value is measured through experiments.

[0085] Table 1 Properties of modified alkyl glycoside inhibitors prepared in Examples 1-5 of the present invention

[0086]

[0087] From the data in Table 1, it can be seen that after high-temperature aging at 240°C for 16 hours, in the embodiment, the relative inhibition rate of the 0.7% modified alkyl polyglycoside high-temperature strong inhibitor product sample on calcium soil is greater than 96%, showing good high-temperature inhibition and anti-collapse performance; the modified alkyl polyglycoside sample EC 50 Value> 500000mg / L (far greater than the emission standard of 30000mg / L), no biological toxicity, green and environmentally friendly. In comparative examples 1-2, the relative inhibition rates of 0.7% modified alkyl polyglycoside samples on calcium soil were 85.54% and 39.35% respectively; in comparative examples 1-2, the EC of modified alkyl polyglycoside samples 50 The values ​​are 487200mg / L and 124300mg / L respectively.

[0088] The modified alkyl polyglycoside prepared in the embodiment of the present invention has good high temperature resistance and strong inhibition performance; at the same time, it has no biological toxicity and is green and environmentally friendly. The modified alkyl polyglycoside prepared in the embodiment of the present invention is suitable for drilling construction in deep wells and ultra-deep wells with high formation temperatures in highly water-sensitive shale, mudstone, mudstone interlayers and other easily collapsed formations, meeting the requirements of well wall stability and green environmental protection in high-temperature formations.

[0089] The above descriptions are only preferred embodiments of the present invention. It should be pointed out that professionals in this technical field can implement various modifications to these embodiments without departing from the technical principles of the present invention, and these modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A modified alkyl polyglycoside high temperature resistant strong inhibitor, characterized in that: Includes groups with structures shown below: The groups shown in formula II, formula III, formula IV and formula V are grafted onto the structure of formula I; Among them, R1 is a C1-6 alkyl group; R2 is a C0-2 alkylene group; R3 is a C0-1 alkylene group, and R4 is a nitrogen-containing C2-8 straight carbon chain or a C0-1 alkylene group; n is the degree of polymerization, and n does not exceed 800; the group shown in formula IV is an ethylenediamine residue, a propylenediamine residue or a polyethylenepolyamine residue.

2. The method for preparing the modified alkyl polyglycoside high temperature resistant strong inhibitor according to claim 1, characterized in that: The following steps are involved: S1, mixing an alkyl glucoside, a halogenated epoxide and a polymeric diol and reacting them to obtain a halogenated alcohol polyether alkyl glucoside; S2, reacting the halogenated alcohol polyether alkyl glycoside with an organic amine to obtain an amino polyether alkyl glycoside; S3, reacting the amino polyether alkyl polyglycoside with aminosulfonic acid to obtain a modified alkyl polyglycoside high temperature resistant strong inhibitor.

3. The preparation method according to claim 2, characterized in that: The alkyl glycoside is methyl glycoside, ethyl glycoside, propyl glycoside, butyl glycoside or hexyl glycoside; the halogenated epoxide is epichlorohydrin or epichlorohydrin.

4. The preparation method according to claim 2, characterized in that: The polymeric diol is polyethylene glycol with a degree of polymerization not exceeding 800.

5. The preparation method according to claim 2, characterized in that: The reaction in step S1 is carried out in the presence of a first catalyst, and the first catalyst is an acidic catalyst.

6. The preparation method according to claim 2, characterized in that: The organic amine is ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or pentaethylenehexamine.

7. The preparation method according to any one of claims 2 to 6, characterized in that: The reaction in step S3 is carried out in the presence of a second catalyst, wherein the second catalyst is one or more of urea, ethylurea and thiourea.

8. The preparation method according to claim 7, characterized in that: The reaction temperature in step S3 is 40-60° C., and the reaction time is more than 30 minutes.

9. Use of the modified alkyl polyglycoside high temperature resistant strong inhibitor as claimed in claim 1 in preparing drilling fluid.

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