Organic silicon emulsifier for oil-in-water drilling fluid and preparation method of organic silicon emulsifier

Abstract

The invention discloses an organic silicon emulsifier for oil-in-water drilling fluid and a preparation method of the organic silicon emulsifier, and belongs to the technical field of petroleum assistants. The organic silicon emulsifier is an organic silicon surfactant prepared by taking organic silicon phenyl alcohol, a cyano-containing phenyl isocyanate compound and hydroxyl-containing alkyl sodium carboxylate as reaction raw materials; and the emulsifier is used as an oil-in-water drilling fluid. The organic silicon emulsifier is outstanding in temperature resistance, small in foaming effect and high in emulsifying property, and can be used for a temperature-resistant oil-in-water drilling fluid system, so that the obtained oil-in-water drilling fluid system has excellent temperature resistance while having the characteristics of conventional water-based drilling fluid.

Description

Technical Field

[0001] The present invention relates to the technical field of petroleum additives, and particularly relates to an organosilicon emulsifier for oil-in-water drilling fluid and a preparation method thereof. Background Art

[0002] In recent years, with the continuous growth of the global demand for fossil energy, the exploration and development direction of oil and gas resources has gradually shifted from shallow wells and medium-deep wells to complex wells such as deep wells and extended-reach wells. Especially, the rapid development of unconventional oil and gas resources mainly dominated by shale gas has set off a new wave of drilling revolution. During the drilling process of shale gas wells, due to the water sensitivity of hard and brittle shale, wellbore instability often occurs, and conventional water-based drilling fluids can no longer meet the technical requirements of drilling operations. Under this background, oil-based drilling fluids (mainly including full oil-based drilling fluids and water-in-oil drilling fluids) have gradually replaced water-based drilling fluids and are applied to the shale section of shale gas wells due to their advantages such as strong temperature and salt resistance, good lubricity, and no water sensitivity. However, full oil-based drilling fluids and water-in-oil drilling fluids with oil as the continuous phase have defects such as high cost, poor environmental protection performance, and weak water invasion resistance, which to a certain extent limit their popularization and application. In contrast, oil-in-water drilling fluids not only have the advantages of simple maintenance, controllable cost, acceptable environmental protection performance, and strong water invasion resistance of water-based drilling fluids, but also have the characteristics of strong temperature and salt resistance and good lubrication performance of oil-based drilling fluids. Therefore, they have gradually attracted the attention of scientific research institutions in the field and have been gradually promoted to field applications.

[0003] The oil-in-water drilling fluid system is a drilling fluid system with water as the continuous phase and oil as the dispersed phase. The key to the stability of the oil-in-water drilling fluid system lies in the selection of the emulsifier. The main function of the emulsifier is to reduce the interfacial tension between the oil phase and the water phase. After adding the emulsifier to the oil and water phases, due to the amphiphilic structure of the emulsifier, the lubricant molecules are closely arranged on the interface between the oil phase and the water phase, forming a film with high strength and excellent viscoelasticity, greatly reducing the interfacial tension of the film, weakening the remaining interfacial free energy on the film, and thus forming a stable emulsion. The interfacial film constructed by the emulsifier can protect the dispersed phase liquid and weaken the mutual collision between the liquids, thereby avoiding the aggregation of droplets. Currently, the HLB value of the emulsifier used in the oil-in-water drilling fluid system is between 8 and 18, that is, the hydrophilicity of this type of emulsifier is higher than the lipophilicity, and the thickness of the outer phase hydration film is greater than the thickness of the inner phase oil solvation film. Typical emulsifiers include: polyamide emulsifiers, alkanolamide emulsifiers, alkyl primary alcohol emulsifiers, polyesteramide emulsifiers, maleic rosin emulsifiers, polyether emulsifiers, as well as soaps of carboxylic acids, soaps of sulfonic acids, and organic acid esters, etc.

[0004] However, at present, in order to make the emulsion droplets formed in the oil-in-water drilling fluid more stable, the emulsifiers used are mostly composite emulsifiers, that is, generally a single surfactant is not used as an emulsifier; in addition, the temperature resistance of such emulsifiers generally does not exceed 160 °C, and there are few literature reports on emulsifiers with a temperature resistance of up to 180 °C. The above technical defects limit the application range of the oil-in-water drilling fluid. Summary of the Invention

[0005] The purpose of the present invention is to provide an organosilicon emulsifier for oil-in-water drilling fluid and a preparation method thereof. The emulsifier can be used as a single emulsifier in the oil-in-water drilling fluid system, and the formed emulsion droplets are stable and have good temperature resistance.

[0006] The present invention is achieved through the following technical solutions:

[0007] An organosilicon emulsifier for oil-in-water drilling fluid, the structural formula of the emulsifier is shown in formula (I):

[0008]

[0009] Among them, the structural formula of T in the structural formula (I) is shown in formula (II):

[0010]

[0011] Among them, R1 and / or R2 in formula (II) are selected from one of H or C1-C6 alkyl;

[0012] x represents the number of —CH 2 — structural units in the alkyl, which is a natural number from 0 to 18, preferably a natural number from 0 to 6;

[0013] M in the structural formula (II) 1 、M 2 、M 3 、M 4 and M 5 At least one of them has the structure shown in formula (III), and the rest are all one of H or C1-C6 alkyl,

[0014]

[0015] Preferably, 1-3 of M 1 、M 2 、M 3 、M 4 and M 5 have the structure shown in formula (III), and the rest are all H.

[0016] Preferably, R 3 and / or R 4One selected from H or C1-C12 alkyl.

[0017] Preferably, y represents the number of —CH 2 — structural units in the alkyl group in formula (III), which is a natural number from 0 to 18, preferably a natural number from 0 to 12.

[0018] In the present invention, a preparation method of an organosilicon emulsifier is also provided.

[0019] According to the present invention, the preparation method of the organosilicon emulsifier comprises the following steps:

[0020] First step, dissolve the compound shown in the structural formula (IV) in solvent I, heat it, and then add catalyst a and the compound shown in the structural formula (V) under the protection of an inert gas, react for 4-16 h, preferably 8-12 h, and then carry out purification treatment to obtain intermediate M;

[0021]

[0022] Among them, in the structural formula (IV), R 1 and / or R 2 is selected from one of H or C1-C6 alkyl;

[0023] In the structural formula (IV), x represents the number of —CH 2 — structural units in the alkyl group, which is a natural number from 0 to 18,

[0024] Among them, in the structural formula (V), K 1 、K 2 、K 3 、K 4 and K 5 at least one of them is CN, and the rest are each one of H or C1-C6 alkyl;

[0025] Step S2, mix intermediate M with the compound shown in the structural formula (VI) and solvent II, heat it, add catalyst b to carry out a reaction, and then carry out purification treatment to obtain the organosilicon emulsifier product,

[0026]

[0027] Among them, R 3 and / or R 4 is selected from one of H or C1-C12 alkyl;

[0028] y represents the number of —CH 2 — structural units in the alkyl group in formula (VI), and y is a natural number from 0 to 18.

[0029] Preferably, in the structural formula (V), K1 , K 2 , K 3 , K 4 and K 5 There are 1 - 3 CNs, and the rest are all H.

[0030] The chemical reaction formula of the above reaction is as follows:

[0031] The first step:

[0032]

[0033] The second step:

[0034]

[0035] In the present invention, in the first step, first, a compound with the structural formula as shown in (IV) is mixed with a first solvent to form a mixed solution A. After heating to 50 - 90 °C, preferably 65 - 75 °C, then under the protection of an inert gas, a catalyst a and a compound with the structural formula as shown in (V) are added to the mixed solution A to form a mixed solution B. The reaction is carried out for 4 - 16 h, preferably 8 - 12 h, and then the first purification treatment is carried out to obtain an intermediate M.

[0036] In the second step, the intermediate M, a compound with the structural formula as shown in (VI), and a second solvent are mixed to form a mixed solution C. Under the protection of an inert gas, it is heated to a predetermined temperature, a catalyst b is added for reaction, and then the second purification treatment is carried out to obtain an emulsifier product.

[0037] In the present invention, the first solvent is one or more of diethyl ether, propylene oxide, ethylene glycol ether, triethanolamine, acetone, butanone, methyl isobutyl ketone, carbon tetrachloride, chloroform, dichloromethane, 1,1 - dichloroethane, 1,2 - dichloroethane, methyl ethyl ketone, tetrahydrofuran, petroleum ether, acetonitrile, ethyl acetate, benzene, toluene, m - xylene, chlorobenzene, cyclohexane, cyclohexanone, toluene cyclohexanone, methyl acetate, ethyl acetate, propyl acetate, nitromethane, 1,4 - dioxane, pyridine, morpholine, N, N - dimethylformamide, N,N - dimethylacetamide, and dimethyl sulfoxide. Preferably, it is one of benzene, toluene, N,N - dimethylformamide, N,N - dimethylacetamide, and dimethyl sulfoxide.

[0038] In the present invention, the concentration of the compound containing the structural formula (IV) in the first solvent is 10 wt% - 20 wt%.

[0039] In the present invention, the molar ratio of the compound containing the structural formula (IV) to the compound containing the structural formula (V) is 1:4 - 6. Considering the reaction efficiency of the reactants and the product yield, the preferred ratio is 1:4.5 - 5.5.

[0040] In the present invention, the catalyst a is preferably dibutyltin dilaurate, and the dosage is 0.04 wt% to 0.24 wt% of the mass of the compound with structural formula (V), and the preferred dosage range is 0.08 wt% to 0.16 wt%.

[0041] In the present invention, the inert gas is one of nitrogen and argon.

[0042] Furthermore, in order to obtain a higher purity intermediate M, the preparation method of the intermediate M provided in the present application further includes a first purification treatment, that is, recrystallization of the crude product of the intermediate M obtained from the synthesis reaction.

[0043] The preferred method is: after vacuum distillation, acetonitrile is added to the pale yellow paste-like crude product, and then toluene is added. After stirring evenly, the temperature is lowered to -28 °C, and bright yellow solids will precipitate out. After filtration and rinsing the solids with toluene, the purified intermediate M is obtained.

[0044] Preferably, the mass ratio of acetonitrile to the pale yellow paste-like crude product is 1:3 to 6.

[0045] Preferably, the mass ratio of toluene to the pale yellow paste-like crude product is 2 to 4:1.

[0046] In the present invention, the solvent two is selected from one or more of diethyl ether, propylene oxide, ethylene glycol ether, triethanolamine, acetone, methyl ethyl ketone, methyl isobutyl ketone, carbon tetrachloride, chloroform, dichloromethane, 1,1-dichloroethane, 1,2-dichloroethane, methyl ethyl ketone, tetrahydrofuran, petroleum ether, acetonitrile, ethyl acetate, benzene, toluene, m-xylene, chlorobenzene, cyclohexane, cyclohexanone, toluene cyclohexanone, methyl acetate, ethyl acetate, propyl acetate, nitromethane, 1,4-dioxane, pyridine, morpholine, N,N-dimethylformamide, N,N-dimethylacetamide and dimethyl sulfoxide. Preferably, they are N,N-dimethylformamide, N,N-dimethylacetamide and dimethyl sulfoxide.

[0047] In the present invention, in the mixed solution C, the concentration of the compound with structural formula (VI) in the solvent two is 2.0 wt% to 20.0 wt%, and the preferred concentration range is 5.0 wt% to 10.0 wt%.

[0048] In the present invention, in the mixed solution C, the molar ratio of the intermediate M to the compound with structural formula (VI) is 1:4 to 15. Considering the product yield, the preferred ratio is 1:4.5 to 12.5.

[0049] In the present invention, the catalyst b is An acid or a Lewis acid, specifically selected from sulfuric acid, phthalimide, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, bismuth trifluoromethanesulfonate, calcium trifluoromethanesulfonate, copper trifluoromethanesulfonate, indium trifluoromethanesulfonate, bis(trifluoromethanesulfonyl)imide, boron trifluoride, boron trifluoride diethyl ether, perfluorosulfonic acid resin, 2,4-dinitrobenzenesulfonic acid, dodecatungstophosphoric acid, acid salt of cesium tungstophosphate (Cs 2.5 H 0.5 PW 12 O 40 )、Cs 2 SO 4 、Ce(SO 4 ) 2 、P 2 O 5 、I 2 、CuCl, CuBr, CuI, CuCl 2 、CoCl 2 、ZnCl 2 and FeCl 3 ·6H 2 O, or one or more of them, preferably boron trifluoride, boron trifluoride diethyl ether, bismuth trifluoromethanesulfonate, calcium trifluoromethanesulfonate, copper trifluoromethanesulfonate, indium trifluoromethanesulfonate, perfluorosulfonic acid resin, CuCl 2 and FeCl 3 ·6H 2 O. More preferably boron trifluoride diethyl ether, bismuth trifluoromethanesulfonate, calcium trifluoromethanesulfonate, copper trifluoromethanesulfonate, indium trifluoromethanesulfonate.

[0050] In the present invention, the catalyst b is 0.02% - 12.0% of the total molar amount of the intermediate M and the compound containing the structural formula (VI), preferably 0.5% - 10.0%, and more preferably 2.0% - 5.0%.

[0051] In the present invention, the temperature of the reaction is 80 - 160 °C, preferably 100 - 150 °C.

[0052] In the present invention, the reaction time of the intermediate M and the compound containing the structural formula (VI) is preferably controlled within 4 - 64 h. If the reaction time is too short, the reaction is incomplete, that is, there are still some reaction raw materials in the reaction system that have not participated in the reaction; if the reaction time is too long, by-products will be produced, affecting the product yield. Considering the reaction efficiency and product yield comprehensively, the reaction time of the intermediate M and the compound containing the structural formula (VI) is preferably 8 - 48 h, and more preferably 16 - 28 h.

[0053] Furthermore, in order to obtain an organosilicon emulsifier product with higher purity, the preparation method of the organosilicon emulsifier in this solution further includes a second purification treatment, that is, concentrating, soaking, filtering, washing and drying the crude product of the organosilicon emulsifier obtained from the synthesis reaction.

[0054] In the present invention, in the second purification treatment, concentration can be carried out by vacuum distillation, preferably rotary evaporation under reduced pressure. The soaking time is more than 4 h, preferably 6 - 12 h.

[0055] In the present invention, methanol or ethanol is used for soaking.

[0056] In the present invention, the washing is carried out by three times of rinsing with methanol or ethanol, acetone, and glacial acetic acid - ethylene glycol with a volume ratio of 3:2 respectively. After washing, drying is carried out, preferably freeze - drying under vacuum until constant weight.

[0057] The present invention provides an application of the above - mentioned silicone emulsifier. The silicone emulsifier can be applied to the field of petroleum engineering. Preferably, the silicone emulsifier is used in an oil - in - water drilling fluid system.

[0058] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0059] 1. In the present invention, the provided silicone emulsifier belongs to a kind of silicone surfactant. A benzene ring is introduced into the molecular chain, which enhances the molecular rigidity, is beneficial to weakening the molecular movement under high - temperature conditions, and thus improves the stability of the interfacial film of emulsion droplets under high - temperature conditions. This silicone emulsifier has strong emulsifying ability, stable emulsion, small foaming effect, and outstanding high - temperature resistance, and can be used in an oil - in - water drilling fluid system with high - temperature resistance. Description of the Drawings

[0060] Figure 1 is the 1 H NMR spectrum of intermediate M1 prepared in Example 1 of the present invention.

[0061] Figure 2 is the 1 H NMR spectrum Detailed Embodiments

[0062] To facilitate the public's understanding of the present invention, the present invention will be further described in detail below with reference to embodiments, but the embodiments of the present invention are not limited thereto.

[0063] Unless otherwise specified, the raw materials and catalysts in the embodiments of the present application are purchased through commercial channels.

[0064] Unless otherwise specified, conventional test methods or test methods recommended by the instruments are adopted.

[0065] The analysis methods in the embodiments of the present application are as follows:

[0066] Nuclear magnetic resonance analysis is carried out using Avance III - 800MHz (Bruker, Switzerland).

[0067] The calculation method of the yield R of the intermediate M or the organosilicon emulsifier in the examples of the present application is as follows:

[0068] R=H 1 / H 0 ×100%,

[0069] R——yield of intermediate M or silicone emulsifier;

[0070] H 0 ——Theoretical mass of intermediate M or silicone emulsifier;

[0071] H 1 ——The measured mass of the intermediate M or the organosilicon emulsifier (the mass of the intermediate M or the organosilicon emulsifier after purification).

[0072] Example 1

[0073] In a reactor equipped with a temperature control device, a reflux condenser and a constant pressure feeding device, 45.66 g (0.1 mol) of tetrakis (4-hydroxymethylphenyl) silane (R 1 , R 2 All H) were dissolved in 400 mL toluene, heated in a water bath to 68°C, and nitrogen was introduced. Under nitrogen protection, 0.08 g of dibutyltin dilaurate and 79.08 g (0.5 mol) of 4-cyanobenzyl isocyanate (x = 1, K 1 , K 2 , K 4 and K 5 For H, K 3 The reaction was continued for 10 h. After filtration, the mixture was allowed to stand and distilled under reduced pressure to obtain 94.24 g of a crude product of a light yellow paste intermediate.

[0074] To the crude product of the light yellow paste intermediate, add 23.5 g of acetonitrile and then add 280 g of toluene. After stirring evenly, cool to -28°C, and a bright yellow solid precipitates. Filter and rinse the solid with toluene to obtain a purified intermediate, recorded as M1, with a calculated yield of 63.50%.

[0075] 56.07 g (0.25 mol) of sodium 10-hydroxyundecyl carboxylate (R 3 For H, R 4 CH 3 , y=8), 27.23g (0.05mol) M1 and 500mL dimethyl sulfoxide, stir thoroughly until dissolved, introduce nitrogen, raise the temperature to 105°C, add 1.7g (0.012mol) boron trifluoride etherate, and continue the reaction under stirring conditions for 24h.

[0076] After the reaction was completed, dimethyl sulfoxide was removed by vacuum distillation. The above product was soaked in a methanol solution for 8 h, filtered by suction, and rinsed with methanol, acetone, and glacial acetic acid - ethylene glycol with a volume ratio of 3:2, and then dried in vacuo to constant weight to obtain the emulsifier product, denoted as C1, with a yield of 60.28%.

[0077] The chemical reaction equation for preparing M1 is as follows:

[0078]

[0079] The chemical reaction equation for preparing C1 is as follows:

[0080]

[0081] The M1 and C1 obtained in Example 1 were characterized by NMR [(CD 3 ) 2 SO, 25 °C], and the nuclear magnetic resonance spectra ( 1 H NMR) are shown in Figure 1 and Figure 2 respectively. According to the analysis of its 1 H NMR, it can be seen that M1 and C1 with the described structures were obtained in this application.

[0082] Example 2

[0083] In a reactor equipped with a temperature control device, a reflux condenser, and a constant-pressure feeding device, 68.1 g (0.1 mol) of tetra(4-(2-(2-hydroxy-3-methylbutyl))phenyl)silane (R 1 is CH 3 , R 2 is CH(CH 3 ) 2 ) was dissolved in 320 mL of N,N-dimethylformamide, heated in a water bath to 71 °C, and nitrogen gas was introduced. Under the protection of nitrogen gas, 0.071 g of dibutyltin dilaurate and 88.74 g (0.45 mol) of 3,5-dicyanophenethyl isocyanate (x = 2, K 1 , K 3 and K 5 are all H, K 2 , K 4 are all CN) were added, and the reaction was continued for 8 h. After suction filtration and standing, vacuum distillation was carried out to obtain 114.9 g of a crude product of a pale yellow paste-like intermediate.

[0084] 38.3 g of acetonitrile was added to the crude product of the pale yellow paste-like intermediate, and then 230 g of toluene was added. After stirring evenly, the temperature was lowered to -28 °C, and bright yellow solids precipitated out. The solids were filtered and rinsed with toluene to obtain the purified intermediate, denoted as M2, with a yield of 62.79%.

[0085] In a reactor equipped with a temperature control device, a reflux condenser and a constant pressure feeding device, 56.74 g (0.45 mol) of sodium 2-hydroxybutyrate (R 3 is H, R 4 is CH 2 CH 3 , y = 0), 73 g (0.05 mol) of M1 and 500 mL of N,N-dimethylformamide were added. After stirring well until dissolved, nitrogen was introduced, the temperature was raised to 105 °C, and 16.4 g (0.025 mol) of bismuth trifluoromethanesulfonate was added. The reaction was continued for 16 h under stirring conditions.

[0086] After the reaction was completed, N,N-dimethylformamide was removed by distillation under reduced pressure. The above product was soaked in an ethanol solution for 6 h, filtered by suction, and rinsed with ethanol, acetone and glacial acetic acid-ethylene glycol with a volume ratio of 3:2 respectively, and dried in vacuo to constant weight to obtain an emulsifier product, denoted as C2, with a yield of 64.85%.

[0087] The chemical reaction formula is as follows:

[0088]

[0089]

[0090] Example 3

[0091] In a reactor equipped with a temperature control device, a reflux condenser and a constant pressure feeding device, 56.88 g (0.1 mol) of tetrakis(4-(1-hydroxypropyl)phenyl)silane (R 1 is H, R 2 is CH 2 CH 3 ) was dissolved in 460 mL of dimethyl sulfoxide, and the mixture was heated in a water bath to 75 °C, and nitrogen was introduced. Under the protection of argon gas, 0.26 g of dibutyltin dilaurate and 166.99 g (0.6 mol) of 2,4,6-tricyanobenzenehexyl isocyanate (x = 6, K 2 , K 4 are both H, K 1 , K 3 and K 5 are both CN) were added, and the reaction was continued for 12 h. After filtration by suction and standing, distillation under reduced pressure was carried out to obtain 129 g of a crude product of a pale yellow paste-like intermediate.

[0092] 21.5 g of acetonitrile was added to the crude product of the pale yellow paste-like intermediate, and then 516 g of toluene was added. After stirring evenly, the temperature was lowered to -28 °C, and bright yellow solids precipitated out. The solids were filtered and rinsed with toluene to obtain a purified intermediate, denoted as M2, with a yield of 64.11%.

[0093] In a reactor equipped with a temperature control device, a reflux condenser device, and a constant pressure feeding device, 324.28 g (0.625 mol) of sodium 20-hydroxytritriacontanoate (R 3 is H, R4 is CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 , y = 18), 84.1 g (0.05 mol) of M1 and 5000 mL of N,N-dimethylacetamide were added. After stirring well until dissolved, argon was introduced, the temperature was raised to 150 °C, and 4.88 g (0.0135 mol) of copper trifluoromethanesulfonate was added. The reaction was continued for 28 h under stirring conditions.

[0094] After the reaction was completed, N,N-dimethylacetamide was removed by vacuum distillation. The above product was immersed in a methanol solution for 12 h, filtered by suction, and rinsed with methanol, acetone, and glacial acetic acid-ethylene glycol with a volume ratio of 3:2 respectively, and then dried in vacuo to constant weight to obtain an emulsifier product, denoted as C3, with a yield of 54.75%.

[0095] The chemical reaction formula is as follows:

[0096]

[0097] Example 4

[0098] In a reactor equipped with a temperature control device, a reflux condenser device, and a constant pressure feeding device, 51.27 g (0.1 mol) of tetrakis(4-(1-hydroxyethyl)phenyl)silane (R 1 is H, R 2 is CH 3 ) was dissolved in 360 mL of N,N-dimethylacetamide, and the mixture was heated in a water bath to 65 °C, and nitrogen was introduced. Under the protection of nitrogen gas, 1.19 g of dibutyltin dilaurate and 79.27 g (0.55 mol) of 3-cyanophenyl isocyanate (x = 0, K 1 , K 2 , K 3 and K 5 are all H, K 4 is CN) were added, and the reaction was continued for 11.5 h. After filtration by suction and standing, vacuum distillation was carried out to obtain 76.8 g of a crude product of a pale yellow paste-like intermediate.

[0099] 15.36 g of acetonitrile was added to the crude product of the pale yellow paste-like intermediate, and then 240 g of toluene was added. After stirring evenly, the temperature was lowered to -28 °C, and bright yellow solids precipitated. After filtration and rinsing the solids with toluene, the purified intermediate, denoted as M1, was obtained with a yield of 62.07%.

[0100] 25.21 g (0.225 mol) of sodium 2-hydroxypropionate (R 3 is H, R 4 is CH 3 , y = 0), 54.46 g (0.05 mol) of M1 and 380 mL of dimethyl sulfoxide were added to a reactor equipped with a temperature control device, a reflux condenser and a constant pressure feeding device. After stirring well until dissolved, nitrogen was introduced, the temperature was raised to 129 °C, and 7.11 g (0.01265 mol) of indium trifluoromethanesulfonate was added. The reaction was continued for 20 h under stirring.

[0101] After the reaction was completed, dimethyl sulfoxide was removed by distillation under reduced pressure. The above product was immersed in an ethanol solution for 10 h, filtered by suction, rinsed with ethanol, acetone and glacial acetic acid-ethylene glycol with a volume ratio of 3:2 respectively, and dried in vacuo to constant weight to obtain the emulsifier product, denoted as C4, with a yield of 62.25%.

[0102] The chemical reaction formula is as follows:

[0103]

[0104] Example 5

[0105] The emulsifier was prepared according to the method of Example 1, except that tetrakis(4-hydroxymethylphenyl)silane was replaced with an equimolar amount of tetrakis(4-(1-hydroxycyclohexyl)phenyl)silane (R 1 is H, R 2 is cyclohexyl), 4-cyanobenzyl isocyanate was replaced with an equimolar amount of 2-cyanopropyl isocyanate (x = 3, K 2 、K 3 、K 4 and K 5 are all H, K 1 is CN), toluene was replaced with an equal volume of benzene, and sodium 10-hydroxyundecanoate was replaced with sodium 2-hydroxy-2-methylhexanoate (R 3 、R 4 are both CH 3 , y = 3), to obtain the emulsifier, denoted as C5, with a yield of 61.77%.

[0106] Example 6

[0107] Prepare the emulsifier according to the method of Example 1, except that tetrakis(4-hydroxymethylphenyl)silane is replaced with an equimolar amount of 4-cyanobenzyl isocyanate replaced with an equimolar amount of 2,6-dicyanobenzyl isocyanate (x = 1, K 2 、K 3 、K 4 are all H, K 1 and K 5 are both CN), the water bath heating temperature is replaced from 68 °C to 72 °C, and sodium 10-hydroxyundecanoate (R 3 is H, R 4 is CH 3 , y = 8) is replaced with sodium 2-hydroxy-2-methylpropionate (R 3 、R 4 are both CH 3 , y = 0), denoted as C6, with a yield of 62.3%.

[0108] Example 7

[0109] Prepare the emulsifier according to the method of Example 1, except that the molar amount of 4-cyanobenzyl isocyanate is changed from 0.5 mol to 0.4 mol, and the molar amount of sodium 10-hydroxyundecanoate is changed from 0.25 mol to 0.2 mol. The yield of the crude product M7 obtained is 35.48%, and the yield of the emulsifier product C7 obtained is 31.72%. The yield of the emulsifier product C7 is significantly lower than that of C1 in Example 1.

[0110] Example 8

[0111] Prepare the emulsifier according to the method of Example 1, except that the molar amount of 4-cyanobenzyl isocyanate is changed from 0.5 mol to 0.6 mol, and the molar amount of sodium 10-hydroxyundecanoate is changed from 0.25 mol to 0.75 mol. The yield of the crude product M8 obtained is 36.10%, and the yield of the emulsifier product C8 obtained is 32.19%. The yield of the emulsifier product C8 is significantly lower than that of C1 in Example 1.

[0112] Comparative Example 1

[0113] Prepare the emulsifier according to the method of Example 1, except that tetrakis(4-hydroxymethylphenyl)silane is replaced with an equimolar amount of tetrakis(4-hydroxymethylphenyl)methane to obtain the emulsifier, denoted as D1, with a yield of 65.21%.

[0114] Comparative Example 2

[0115] Prepare the emulsifier according to the method of Example 1, except that tetrakis(4-hydroxymethylphenyl)silane is replaced with 4-fold molar amount of hydroxyhexyltrimethylsilane to obtain the emulsifier, denoted as D2, with a yield of 60.48%.

[0116] Test Example 1

[0117] The interfacial tension was determined by mixing 0 # Diesel oil and water were mixed, and silicone emulsifiers C1-C6, D1, D2, nonylphenol polyoxyethylene ether (NP-10) and octylphenol polyoxyethylene ether (OP-10) were added under stirring conditions at a concentration of 2.0wt% to prepare the base slurry of water-in-oil drilling fluid. The oil-water interfacial tension of different experimental slurries was measured using a JYW-200A automatic surface interfacial tension meter. The test results are shown in Table 1:

[0118] Table 1 Oil-water interfacial tension test results

[0119]

[0120] As can be seen from Table 1, after adding C1-C6, D1, D2, NP-10 and OP-10, the oil-water interfacial tension decreased significantly, indicating that the addition of emulsifiers helps to reduce the oil-water interfacial tension. In comparison, the oil-water interfacial tension of the experimental slurry with C1-C6 added is significantly lower than that of the experimental slurry with D1, D2, NP-10 and OP-10 added, indicating that C1-C6 is conducive to the formation of water-in-oil emulsions in the experimental slurry.

[0121] Test Example 2

[0122] Emulsification performance test

[0123] (1) Conductivity test

[0124] According to the volume ratio of 1:1, # Diesel oil and water were mixed, and emulsifiers C1-C6, D1, D2, NP-10 and OP-10 were added under stirring conditions at a concentration of 2.0wt% to prepare the base slurry of water-in-oil drilling fluid. The conductivity of different experimental slurries was measured using an SG7 conductivity meter. The test results are shown in Table 2:

[0125] Table 2 Conductivity test results

[0126]

[0127] As can be seen from Table 2, the conductivity of the experimental pulp with C1 to C6 added is similar to that of water (5.50 μS·cm -1 ), while the conductivity of the experimental pulps with D1, D2, NP-10 and OP-10 was quite different from that of water, indicating that the stability of the emulsion added to the experimental pulps with C1 to C6 was better.

[0128] (2) Water separation time test

[0129] (The test method is from: Yu Tao, Liu Huasha, Wang Chaoqun, etc. Emulsifying properties of alkyl aryl sulfonates for alkanes [J]. Chinese Journal of Applied Chemistry, 2011, 28(5), 560 - 564.)

[0130] The emulsifying properties of surfactants were determined by the water separation time method. An emulsifier solution with a concentration of 2.0% was prepared with pure water. At 25 °C, 40 mL of the emulsifier solution and 40 mL of 0 # diesel were pipetted into a 100 mL stoppered graduated cylinder. The stopper was tightened, and the cylinder was shaken vigorously up and down 10 times, then left to stand for 1 min. This operation was repeated 5 times. The stoppered graduated cylinder was placed on a horizontal tabletop, and the time taken for 10 mL of water to separate at the bottom was recorded. Three parallel groups were repeated, and the average value was taken as an evaluation of the emulsifying properties of the emulsifier. The longer the water separation time, the better the emulsifying properties of the emulsifier. The experimental results are shown in Table 3:

[0131] Table 3 Results of water separation time measurement

[0132]

[0133] As can be seen from Table 3, the water separation time of the experimental slurry with C1 - C6 added is significantly higher than that of the experimental slurry with D1, D2, NP - 10, and OP - 10 added, indicating that adding C1 - C6 has better emulsifying properties for diesel in the experimental slurry. #

[0134] (3) High - temperature resistance test

[0135] Diesel and water were mixed in a volume ratio of 1:1, and emulsifiers C1 - C6, D1, D2, NP - 10, and OP - 10 were added under stirring conditions at a concentration of 2.0 wt% to prepare the base slurry of the oil - in - water drilling fluid as the experimental slurry. The experimental slurry was poured into a high - temperature aging tank and rolled in a roller heating furnace at different temperature conditions for 16 h. After cooling, it was taken out, poured into a 100 mL graduated cylinder, left to stand for 5 days, and the water separation amount was measured. The larger the water separation amount, the weaker the high - temperature stability. #

[0136] The experimental results are shown in Table 4:

[0137] Table 4 Results of water separation amount measurement

[0138]

[0139]

[0140] ​​As can be seen from Table 4, under various aging temperature conditions, the water separation amount of the experimental slurries with C1 - C6 added is significantly lower than that of the experimental slurries with D1, D2, NP - 10, and OP - 10 added, indicating that adding C1 - C6 has good temperature resistance. And under the condition of a temperature of 180 °C, the water absorption amounts of the groups corresponding to the experimental slurries of C1 - C6 are all not higher than 1.7 mL. It can be seen that by using the silicone emulsifier of this single - solution scheme, the temperature resistance can reach 180 °C, and the silicone emulsifier has excellent temperature resistance.

[0141] Test Example 3

[0142] Foaming performance test

[0143] An emulsifier is a surfactant with foaming and foam - stabilizing properties. When used as a drilling fluid additive, it is required that the foaming performance of the emulsifier is as poor as possible, otherwise it will have a negative impact on the rheology and water - injection efficiency of the drilling fluid. In this test example, the Waring - Blender method (stirring method) is used to measure the foaming performance of the emulsifier. Pour 200 mL of an emulsifier solution with a concentration of 2.0% into a tall - stemmed glass. After standing at room temperature for 1 h, pour it into a Waring blender and continuously stir at 10000 r / min for 1 min, then pour it into a 2000 mL graduated cylinder, and record the initial volume of the foam (V0), the foam system volume after 2.5 min (V2.5), and the foam volume after 5.0 min (V5). The test results are shown in Table 5.

[0144] Table 5 Results of foaming performance measurement

[0145]

[0146] As can be seen from Table 5, the V 0 , V 2.5 and V 5 of the experimental slurries with C1 - C6 added are slightly lower than the V 0 , V 2.5 and V 5 of the experimental slurry with D1 added, but significantly lower than the V 0 , V 2.5 and V 5 of the experimental slurries with D2, NP - 10, and OP - 10 added, indicating that the foaming ability of the experimental slurries with C1 - C6 added is relatively weak.

[0147] From the above tests, it can be known that by using the formula and method of the present invention, an emulsifier suitable for the oil - in - water drilling fluid base slurry can be prepared, and its emulsifying performance is better than that of existing emulsifiers such as nonylphenol polyoxyethylene ether (NP - 10) and octylphenol polyoxyethylene ether (OP - 10); at the same time, for the silicone emulsifier in this solution, under the condition of a temperature of 180 °C, the water absorption amount is not higher than 1.7 mL, and it can be used alone, having excellent temperature resistance.

[0148] As described above, it is only a preferred embodiment of the present invention and does not impose any formal limitations on the present invention. Any simple modification or equivalent change made to the above embodiments based on the technical essence of the present invention shall fall within the protection scope of the present invention.

Claims

1. An organosilicon emulsifier for oil-in-water drilling fluid, Characterized in that: The structural formula of the organosilicon emulsifier is shown in formula (I): Among them, the structural formula of T in structural formula (I) is shown in formula (II): Among them, R in formula (II) 1 and / or R 2 is selected from one of H or C1-C6 alkyl; x represents —CH in the alkyl 2 — the number of structural units, which is a natural number from 0 to 18; M in the structural formula (II) 1 , M 2 , M 3 , M 4 and M 5 At least one of them has the structure shown in formula (III), and the rest are each one of H or C1-C6 alkyl y represents the number of —CH 2 — structural units of the alkyl group in formula (III), and is a natural number from 0 to 18; 2 ​ R 3 and / or R 4 selected from one of H or C1-C12 alkyl groups.

2. The organosilicon emulsifier for oil-in-water drilling fluid according to claim 1, Characterized in that: x represents the number of —CH 2 — structural units in the alkyl group, which is a natural number from 0 to 6. 2 ​ 3. The organosilicon emulsifier for oil-in-water drilling fluid according to claim 1, Characterized in that: M in the structural formula (II) 1 , M 2 , M 3 , M 4 and M 5 One to three of them have the structure shown in formula (III), and the rest are all H.

4. The organosilicon emulsifier for oil-in-water drilling fluid according to claim 1, Characterized in that: y is a natural number from 0 to 12.

5. A preparation method of an organosilicon emulsifier for oil-in-water drilling fluid, Characterized in that, Preparing the organosilicon emulsifier according to claim 1, including the following steps: S1. Dissolve the compound shown in structural formula (IV) in solvent I, heat, and then add catalyst a and the compound shown in structural formula (V) under the protection of inert gas, react for 4 to 16 hours, and then carry out purification treatment to obtain intermediate M; Among them, in the structural formula (IV), R 1 and / or R 2 is selected from one of H or C1-C6 alkyl; In the structural formula (IV), x represents the number of —CH 2 — structural units in the alkyl group, which is a natural number from 0 to 18, Among them, in the structural formula (V), K 1 , K 2 , K 3 , K 4 and K 5 at least one of them is CN, and the rest are each one of H or C1-C6 alkyl; S2. Mix intermediate M with the compound shown in structural formula (VI) and solvent II, heat, add catalyst b to carry out the reaction, and then carry out purification treatment to obtain the organosilicon emulsifier product, wherein, R 3 and / or R 4 is selected from one of H or C1-C12 alkyl; y represents the number of —CH 2 — structural units of the alkyl group in formula (VI), and y is a natural number from 0 to 18. 2 ​ 6. The preparation method of the organosilicon emulsifier for oil-in-water drilling fluid according to claim 5, Characterized in that: In step S1, the heating temperature is 50 to 90 °C.

7. The preparation method of the organosilicon emulsifier for oil-in-water drilling fluid according to claim 5, Characterized in that: In step S1, the solvent I is one or more of ether, propylene oxide, ethylene glycol ether, triethanolamine, acetone, butanone, methyl isobutyl ketone, carbon tetrachloride, chloroform, dichloromethane, 1,1-dichloroethane, 1,2-dichloroethane, methyl ethyl ketone, tetrahydrofuran, petroleum ether, acetonitrile, ethyl acetate, benzene, toluene, m-xylene, chlorobenzene, cyclohexane, cyclohexanone, toluene cyclohexanone, methyl acetate, ethyl acetate, propyl acetate, nitromethane, 1,4-dioxane, pyridine, morpholine, N,N-dimethylformamide, N,N-dimethylacetamide and dimethyl sulfoxide.

8. The preparation method of the organosilicon emulsifier for oil-in-water drilling fluid according to claim 7, Characterized in that: In step S1, the solvent I is one of benzene, toluene, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide.

9. The preparation method of the organosilicon emulsifier for oil-in-water drilling fluid according to claim 5, Characterized in that: In step S1, the mass percentage concentration of the solvent I is 10wt% to 20wt%.

10. The preparation method of the organosilicon emulsifier for oil-in-water drilling fluid according to claim 5, Characterized in that: In step S1, the molar ratio of the compound containing structural formula (IV) to the compound containing structural formula (V) is 1:4 to 6.

11. The preparation method of the organosilicon emulsifier for oil-in-water drilling fluid according to claim 10, Characterized in that: In step S1, the molar ratio of the compound containing the structural formula (IV) to the compound containing the structural formula (V) is 1:4.5 to 5.

5.

12. A method for preparing an organosilicon emulsifier for oil-in-water drilling fluid according to claim 5, characterized in that: In step S1, the catalyst a is dibutyltin dilaurate, and the dosage is 0.04 wt% to 0.24 wt% of the mass of compound V.

13. A method for preparing an organosilicon emulsifier for oil-in-water drilling fluid according to claim 5, characterized in that, In step S1, the purification method of intermediate M is: After vacuum distillation, acetonitrile is added to the pale yellow paste-like crude product, and the mass ratio of acetonitrile to the pale yellow paste-like crude product is 1:3 to 6; then toluene is added, and the mass ratio of toluene to the pale yellow paste-like crude product is 2 to 4:1; after stirring evenly, the temperature is lowered to -28 °C, and bright yellow solid precipitates out. After filtration, the solid is rinsed with toluene to obtain the purified intermediate M.

14. A method for preparing an organosilicon emulsifier for oil-in-water drilling fluid according to claim 5, characterized in that, In step S2, the solvent II is selected from one or more of diethyl ether, propylene oxide, ethylene glycol ether, triethanolamine, acetone, butanone, methyl isobutyl ketone, carbon tetrachloride, chloroform, dichloromethane, 1,1-dichloroethane, 1,2-dichloroethane, methyl ethyl ketone, tetrahydrofuran, petroleum ether, acetonitrile, ethyl acetate, benzene, toluene, m-xylene, chlorobenzene, cyclohexane, cyclohexanone, toluene cyclohexanone, methyl acetate, ethyl acetate, propyl acetate, nitromethane, 1,4-dioxane, pyridine, morpholine, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide.

15. A method for preparing an organosilicon emulsifier for oil-in-water drilling fluid according to claim 14, characterized in that, In step S2, the solvent II is one or more of N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide.

16. A method for preparing an organosilicon emulsifier for oil-in-water drilling fluid according to claim 5, characterized in that, In step S2, the concentration of the compound containing the structural formula (VI) in the solvent II is 2.0 wt% to 20.0 wt%.

17. A method for preparing an organosilicon emulsifier for oil-in-water drilling fluid according to claim 16, characterized in that, In step S2, the concentration of the compound containing the structural formula (VI) in the solvent II is 5.0 wt% to 10.0 wt%.

18. A method for preparing an organosilicon emulsifier for oil-in-water drilling fluid according to claim 5, characterized in that, In step S2, the molar ratio of the intermediate M to the compound containing the structural formula (VI) is 1:4 to 15.

19. A method for preparing an organosilicon emulsifier for oil-in-water drilling fluid according to claim 18, characterized in that, In step S2, the molar ratio of the intermediate M to the compound containing the structural formula (VI) is 1:4.5 to 12.

5.

20. A method for preparing an organosilicon emulsifier for oil-in-water drilling fluid according to claim 5, characterized in that, In step S2, the catalyst b is an acid or a Lewis acid, specifically selected from sulfuric acid, phthalimide, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, bismuth trifluoromethanesulfonate, calcium trifluoromethanesulfonate, copper trifluoromethanesulfonate, indium trifluoromethanesulfonate, bis(trifluoromethanesulfonyl)imide, boron trifluoride, boron trifluoride diethyl etherate, perfluorosulfonic acid resin, 2,4-dinitrobenzenesulfonic acid, dodecatungstophosphoric acid, acid salt of cesium phosphotungstate (Cs 2.5 H 0.5 PW 12 O 40 )、Cs 2 SO 4 、Ce(SO 4 ) 2 、P 2 O 5 、I 2 、CuCl, CuBr, CuI, CuCl 2 、CoCl 2 、ZnCl 2 and FeCl 3 ·6H 2 O, and one or more of them are preferably boron trifluoride, boron trifluoride diethyl etherate, bismuth trifluoromethanesulfonate, calcium trifluoromethanesulfonate, copper trifluoromethanesulfonate, indium trifluoromethanesulfonate, perfluorosulfonic acid resin, CuCl 2 and FeCl 3 ·6H 2 O.

21. The preparation method of an organosilicon emulsifier for oil-in-water drilling fluid according to claim 20, characterized in that: the catalyst b is boron trifluoride ethyl ether, bismuth trifluoromethanesulfonate, calcium trifluoromethanesulfonate, copper trifluoromethanesulfonate, indium trifluoromethanesulfonate.

22. The preparation method of an organosilicon emulsifier for oil-in-water drilling fluid according to claim 5, characterized in that: in step S2, the catalyst b is 0.02% to 12.0% of the total molar amount of the intermediate M and the compound containing the structural formula (VI).

23. The preparation method of an organosilicon emulsifier for oil-in-water drilling fluid according to claim 5, characterized in that: in step S2, the purification treatment method is: concentrating the crude product of the emulsifier obtained from the synthesis reaction, soaking it in methanol or ethanol for more than 4 h, and filtering, washing and drying to obtain the purified organosilicon emulsifier product.

24. The preparation method of an organosilicon emulsifier for oil-in-water drilling fluid according to claim 5, characterized in that: the inert gas is one of nitrogen and argon.

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