CN111116632A - Amino film forming inhibitor for drilling fluid and preparation method thereof - Google Patents

Abstract

The invention discloses an amino film-forming inhibitor for drilling fluid and a preparation method thereof. The structural formula of the amino film forming inhibitor is one of the following two types:

or

The inhibitor can effectively improve the inhibitive performance of the drilling fluid, including inhibiting clay slurrying and inhibiting clay hydration dispersion, and the temperature resistance can reach 150 ℃.

Description

Amino film forming inhibitor for drilling fluid and preparation method thereof

Technical Field

The invention relates to the technical field of drilling, in particular to an amino film-forming inhibitor for drilling fluid and a preparation method thereof.

Background

Shale is the main stratum encountered in drilling engineering, and the inhibition of the slurrying of the shale stratum by improving the drilling fluid is the most important means for maintaining the stability of the well wall of the shale well section. Although the oil-based drilling fluid can inhibit slurry making of a shale stratum to a great extent and more effectively prevent collapse of a shale well section, due to the negative factors of high cost, environmental pollution and the like, the application range of the oil-based drilling fluid is limited, so that technical problems are emphasized by drilling fluid companies at home and abroad on an inhibitor for a water-based drilling fluid at present, namely, the inhibition of the drilling fluid is improved by adding a strong and effective inhibitor into the water-based drilling fluid, and the purpose of maintaining the stability of the well wall of the shale well section is achieved.

The synthesis, characterization and performance evaluation of sodium polyamine serving as an inhibitor for drilling fluid are provided in the document structure and performance of the low-polymer amine shale inhibitor for drilling fluid (drilling fluid and completion fluid 2015, 1 month). The treating agent takes amido as a main adsorption group and ether bond as a secondary adsorption group, so that molecules are flatly laid between clay layers, thereby being beneficial to reducing the formation of clay layer spacing.

Polyamine inhibitor SDPA provided in the literature for the development and application of novel polyamine shale hydration inhibitors (journal of the university of Western's Petroleum (Nature science edition) 2013 months) is a polyetheramine inhibitor and belongs to conventional polyamine inhibitors.

The substance of the inhibitor disclosed in the above documents is that amine groups in molecules form ammonium ions under an alkaline condition (the liquid phase environment of the drilling fluid is alkaline), so that electrostatic adsorption occurs with negatively charged clay surfaces, or ether bonds or hydroxyl groups in the molecules form hydrogen bonds with hydroxyl groups on the clay particle surfaces, and the two types of adsorption belong to reversible physical adsorption, and are easy to desorb under a high temperature condition, so that the inhibition effect is reduced.

Chinese patent CN 103087691 a discloses a strong polyamine inhibitor for drilling fluids and a preparation method thereof, the polyamine inhibitor provided in the patent (rejected) is obtained by reacting an amine compound (polyetheramine, alkylamine, etheramine, tetraethylenepentamine, pentaethylenehexamine or polyethylene polyamine) with an epoxy compound (ethylene oxide or propylene oxide), the reaction mechanism is that the amine group and the epoxy group are subjected to ring opening polymerization under an alkaline condition, and the obtained polymer has a molecular structure similar to that of CN 104017208B, and is polyetheramine. The action mechanism is that amido, ether bond and hydroxyl distributed in a molecular chain are used as adsorption groups to be adsorbed with clay, so that the clay lamellar structure is bound, water molecules are prevented from invading between clay layers, and the hydration of the clay is inhibited.

At present, a polyamine film formation inhibitor obtained by reacting an amine compound with an epoxy compound, as proposed in CN 104017208B, is a polyamine inhibitor, which is mainly adsorbed on the surface of clay particles by taking amine and hydroxyl groups as adsorption groups to form a dense protective film to prevent water molecules from entering, thereby achieving the purpose of blocking hydration of water-sensitive clay, which is similar to the action mechanism of amino silanol. Currently, due to the outstanding inhibitory effect, amino inhibitors and their derivatives are gaining attention and are widely used. The amino silanol is an upgraded product of an amino inhibitor, and a strong adsorption group, namely silicon hydroxyl, is introduced on the basis of the amine inhibitor. The treating agent not only retains the molecular characteristics of the amido inhibitor, but also can lead the introduced silicon hydroxyl to have condensation polymerization reaction with the hydroxyl on the clay, so as to coat clay particles into a film, effectively prevent and slow down the hydration action of the clay surface, achieve the effect of inhibiting the hydration dispersion of the clay, and be beneficial to the stability of the well wall of the water-sensitive clay shale. In contrast, aminopolyols do not rely solely on amino and hydroxyl groups as adsorption groups, and the adsorption of the introduced silicon hydroxyl groups is more beneficial to improving the action effect of the inhibitor.

Chinese patent CN 105670578A discloses an aminosilicol inhibitor, which is a silane substance, wherein the silicon atom is directly connected with hydroxyl, primary amine and secondary amine are distributed on the long alkyl chain, and the key point of the preparation is step 3 in the reaction step, i.e. the reaction of silane with Cl atom and primary amine substance.

The document "evaluation of novel aminosilicone inhibitor performance" (petrochemical application in 2015 12 months) provides a molecular structure of the aminosilicone inhibitor, explains the reaction mechanism, and does not give a specific preparation method. The molecule has silicon hydroxyl as a chemical adsorption group and is provided with a long alkyl chain (R is presumed to be the long alkyl chain), so that the molecule forms a hydrophobic layer on the clay surface, and the hydration of the clay surface is prevented and slowed down.

In the prior amidosilanol inhibitor, Si atoms are directly connected with hydroxyl, and if the inhibitor is exposed in the air, intermolecular polycondensation is easy to occur to influence the product quality, and the effective components are reduced. This is the case with the aminosilicone inhibitors referred to in CN 105670578A. In addition, the synthesis steps of the amino silanol inhibitor related to CN 105670578A are complex, and the cost is high due to the fact that the amino silanol inhibitor relates to an expensive catalyst.

Therefore, the development of a high-efficiency inhibitor capable of preventing clay hydration dispersion and inhibiting hydration swelling is a technical problem to be solved at present.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides an amino film-forming inhibitor for drilling fluid and a preparation method thereof. Siloxane is introduced into molecules, and the sheet structure of the clay is firmly bound together by utilizing the chemical adsorption effect of silicon hydroxyl generated after the siloxane is hydrolyzed and the surface of the clay. Because the adsorption is chemical adsorption, the electrostatic adsorption on the clay surface is firmer than that of amino, thereby more effectively preventing water molecules from entering clay layers, and inhibiting hydration expansion while preventing hydration and dispersion of the clay. The inhibitive performance of the drilling fluid can be effectively improved, including clay slurrying inhibition and clay hydration dispersion inhibition, and the temperature resistance can reach 150 ℃.

The invention aims to provide an amine-based film-forming inhibitor for drilling fluid.

The structural formula of the amino film forming inhibitor is one of the following two types:

x is an integer of 0-5; preferably 0, 1, 2, 3;

y is an integer of 1-10; preferably 1, 2, 3, 4, 5.

Wherein R is₁、R₂And R₃Is selected from-CH₃,-O-CH₃,-O-CH₂-CH₃，-O-CH₂-CH₂-O-CH₃，-O-CH₂-CH₂-O-CH₂-CH₂-O-CH₃Is not simultaneously selected as-CH₃。

The invention also aims to provide a preparation method of the amino film-forming inhibitor for the drilling fluid.

The method comprises the following steps:

fully mixing an amine compound, an alkali metal catalyst and a water removal agent in an alcohol solvent, then adding an epoxy organosilicon compound under the protection of inert gas, boosting the pressure to 0.3-0.5 MPa, reacting, filtering and distilling to obtain the amine film-forming inhibitor;

the molar ratio of the amine compound to the epoxy organosilicon organic compound is 1: (0.5 to 6); preferably 1: (1-3);

the mass of the alkali metal catalyst and the amine compound is 1: (500-800); preferably 1: (500-600);

the mass ratio of the water removing agent to the amine compound is 1: (300-500), preferably 1: (300-400).

The reaction temperature is 70-120 ℃; preferably 90-110 ℃; the reaction time is 1-5 h.

The alkali metal catalyst is preferably one of NaOH and KOH;

the alcohol solvent is preferably one of methanol and ethanol.

The water removal agent can adopt a neutral water removal agent which is conventional in the field, and in the invention, anhydrous CaCl can be preferably selected₂。

The mass percentage concentration of the amine compound in the alcohol solvent is preferably 5.0-20%.

Wherein,

the structural formula of the amine compound is as follows:

x is an integer of 0-5, preferably 0, 1, 2, 3;

y is an integer of 1 to 10, preferably 1, 2, 3, 4, 5.

The structural formula of the epoxy organosilicon compound is as follows:

wherein R is₁、R₂And R₃Is selected from-CH₃，-O-CH₃，-O-CH₂-CH₃，-O-CH₂-CH₂-O-CH₃，-O-CH₂-CH₂-O-CH₂-CH₂-O-CH₃Is not simultaneously selected as-CH₃。

The preparation method comprises the following steps:

fully mixing an amine compound, an alkali metal catalyst and a water removal agent in an alcohol solvent in a sealed reaction container, and heating to 70-120 ℃, preferably 90-110 ℃; then adding epoxy organosilicon compounds under the protection of inert gas, boosting the pressure to 0.3-0.5 MPa, and continuously reacting for 1-5 h; cooling, decompressing and discharging, filtering to remove insoluble matters, decompressing and distilling to remove the alcohol solvent to constant weight to obtain light yellow viscous liquid, namely the amino film-forming inhibitor.

The prepared amino film-forming inhibitor belongs to organosilicon inhibitors, and the amino, hydroxyl and ether bonds in the molecules can be beneficial to improving the adsorption capacity of inhibitor molecules in water-sensitive clay; in addition, Si atoms in molecules are connected with methoxy groups, ethoxy groups or methoxyethoxy groups, and are hydrolyzed in alkaline drilling fluid to generate silicon hydroxyl groups, and then the silicon hydroxyl groups and hydroxyl groups on the surface of the water-sensitive clay are subjected to polycondensation reaction to generate firm chemical adsorption, so that a compact protective film is formed on the surface of the water-sensitive clay; in addition, the molecules entering the clay layers are bound together with the clay lamellar structure under the adsorption action of protonated ammonium positive ions, and silicon hydroxyl in the molecules can also perform polycondensation reaction with hydroxyl among the clay layers, so that the binding effect is firmer, water molecules are more effectively prevented from entering the clay layers, and inhibition of hydration expansion is realized while clay hydration dispersion is prevented.

Drawings

FIG. 1 is a graph of the test data of the slurry forming performance of the sodium bentonite inhibited by the inhibitor, clear water and KCl solution prepared in the example.

Detailed Description

The present invention will be further described with reference to the following examples.

The raw material is from Nanjing Engineers organic silicon materials GmbH, Jiangsu Nanjing; caruncle cheng chemical limited, shandong jingning;

all starting materials are commercially available.

Example 1

In a sealed reaction vessel, 60.1g (1.0mol) of ethylenediamine (x ═ 0), 0.12g of NaOH, and 0.17g of anhydrous CaCl₂Fully mixing the materials in 500mL of ethanol, and heating to 105 ℃; then in N₂472.68g (2.0mol) of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane is added under the protection of (1), the pressure is increased to 0.35MPa, and the reaction is continued for 2.5 h; cooling, decompressing and discharging, filtering to remove insoluble substances, decompressing and distilling to remove ethanol to constant weight to obtain light yellow viscous liquid, namely the amino film-forming inhibitor. The structural formula is as follows:

example 2

In a sealed reaction vessel, 148.2g of EDR148(3, 6-dioxaoctane-1, 8-diamine, 1.0mol) (x. times.2), 0.27g of KOH and 0.42g of anhydrous CaCl₂Fully mixing the components in 1000mL of methanol, and heating to 90 ℃; then in N₂218.37g (1.0mol) of (3-glycidoxypropyl) dimethylethoxysilane is added under the protection of (2), the pressure is increased to 0.5MPa, and the reaction is continued for 2.0 h; cooling, pressure relief, discharging, filteringRemoving insoluble substances, and distilling under reduced pressure to remove methanol to constant weight to obtain light yellow viscous liquid, namely the amino film-forming inhibitor. The structural formula is as follows:

example 3

In a sealed reaction vessel 192.26g (1.0mol)3,6, 9-trioxaundecane-1, 11-diamine (x ═ 3), 0.35g NaOH and 0.6g anhydrous CaCl were added₂Fully mixing in 2000mL of ethanol, and heating to 95 ℃; then in N₂407.74g (1.106mol) of 3- (2, 3-epoxypropoxy) propyl trimethoxy ethoxy silane is added under the protection of (1.106mol), the pressure is increased to 0.43MPa, and the reaction is continued for 4.0 h; cooling, decompressing and discharging, filtering to remove insoluble substances, decompressing and distilling to remove ethanol to constant weight to obtain light yellow viscous liquid, namely the amino film-forming inhibitor.

The structural formula is as follows:

example 4

In a sealed reaction vessel, 103.17g (1.0mol) of diethylenetriamine (y 1), 0.2g of NaOH and 0.3g of anhydrous CaCl₂Fully mixing in 1800mL ethanol, and heating to 105 ℃; then in N₂661.02g (2.66mol) of (3-glycidoxypropyl) methyldiethoxysilane are added under the protection of (2), the pressure is increased to 0.5MPa, and the reaction is continued for 5.0 h; cooling, decompressing and discharging, filtering to remove insoluble substances, decompressing and distilling to remove ethanol to constant weight to obtain light yellow viscous liquid, namely the amino film-forming inhibitor. The structural formula is as follows:

example 5

In a sealed reaction vessel, 232.37g (1.0mol) of pentaethylenehexamine (y 4), 0.4g of NaOH and 0.63g of anhydrous CaCl₂Mix well in 2200mL of methanolHeating to 105 ℃; then in N₂325.77g (1.17mol) of 3- (2, 3-epoxypropoxy) propyltriethoxysilane is added under the protection of (1.3), the pressure is increased to 0.3MPa, and the reaction is continued for 5.0 h; cooling, decompressing and discharging, filtering to remove insoluble matters, decompressing and distilling to remove methanol to constant weight to obtain light yellow viscous liquid, namely the amino film-forming inhibitor. The structural formula is as follows:

example 6

Test for inhibiting hydration dispersion performance of shale by amino film forming inhibitor

(test methods from Brookfield, Li Tao, Zhang Tianxiao, etc. Jinshan gas field Strong inhibition anti-collapse drilling fluid research and application [ J ] scientific technology and engineering, 2014, 14(22), 35-40.)

Placing 40.0g of 6-10-mesh shale debris into a high-temperature aging tank filled with clear water, 7.0% of KCl, 1.0% of polyacrylamide sylvite and 0.3% of the amino film-forming inhibitor for drilling fluid prepared in the embodiments 1-5 respectively, rolling and aging at 90 ℃, 120 ℃ and 150 ℃ for 16.0h, taking out, cooling to room temperature, sieving with a 28-mesh sieve and a 40-mesh sieve successively to recover the debris, drying at 105 ℃ to constant weight, weighing the mass of the debris, and calculating the rolling recovery rate, wherein the experimental results are shown in tables 1-3:

TABLE 1 Rolling recovery of rock debris (90 ℃ C.. times.16 h) for different inhibitors

TABLE 2 Rolling recovery of rock debris (120 ℃ C.. times.16 h) for different inhibitors

TABLE 3 Rolling recovery of rock debris (150 ℃ C.. times.16 h) for different inhibitors

As can be seen from tables 1 to 3, compared with clear water, 7.0% of KCl and 1.0% of polyacrylamide potassium salt, the experimental slurry added with 0.3% of 5 different amine group film-forming inhibitors has higher rolling recovery rate of 28-mesh sieve sieving and higher rolling recovery rate of 40-mesh sieving, and the 5 different amine group film-forming inhibitors prepared by the embodiment of the invention can effectively ensure the integrity of rock debris and are more favorable for improving the stability of the well wall of a drilling well.

Example 7

Test of performance of amino film forming inhibitor for inhibiting sodium bentonite pulping

(the test method is from Brookfield, Li Tao, Wang, and the like, Longfeng mountain air field plugging type anti-collapse drilling fluid [ J ]. drilling fluid and completion fluid, 2016, 33(5), 35-40.)

Clean water, 7.0% of KCl, 0.3% of the amino film-forming inhibitor for the drilling fluid prepared in the embodiment 1-5 and 5.0% of sodium bentonite are quantitatively added into 400mL of tap water, the mixture is stirred at a high speed for 30min, the pH value of the system is adjusted to be more than or equal to 9.0 by using 0.1% of NaOH solution, the 3-turn reading of the experimental slurry is measured after the experimental slurry is hot rolled for 16h at 90 ℃ (the 3-turn reading (the rotation speed of a rotor is 3rmp) is the reading of a six-speed rotational viscometer, and the characteristic is the rheological property under the condition of low shear rate. The larger the reading, the more viscous the drilling fluid and the higher the slurrification rate ]. Then 5.0% sodium bentonite is added, stirred at high speed for 30min, and measured after hot rolling under the same conditions. Repeating the steps until the degree can not be measured. The effect of the 3-turn reading of the experimental slurry at each stage was compared to the effect of the different inhibitors.

Under the condition of the same bentonite addition, the 3-turn reading of the amino film-forming inhibitor for the drilling fluid prepared in the examples 1 to 5 is equivalent and is always maintained at a lower level, which shows that the ability of inhibiting the hydration of sodium bentonite is stronger than that of inhibiting the hydration and pulping of bentonite by using the conventional inhibitor KCl, and is shown in figure 1. (the stronger the slurrification capacity, the greater the 3-revolution reading; although the 3-revolution reading for each sample increased with increasing sodium bentonite addition, the rate of rise of the 3-revolution reading for the amine-based film-forming inhibitor added samples was significantly less than the rate of rise of the 3-revolution reading for the control samples (clear water and KCl) in comparison).

Example 8

Test for inhibiting hydration expansion of sodium bentonite by amino film forming inhibitor

(test methods from: Guowen, Penbo, Miaoweiping, et al. Structure and Performance of Oligoamine-based shale inhibitors for drilling fluids [ J ]. drilling and completion fluids 2015, 32(1), 26-29.)

400mL of tap water was added to a high stirring cup, 32g of clay was added at a certain stirring speed, and 1.6g of Na was added₂CO₃. Stirring for 20min, stopping stirring at least twice during the stirring, scraping off clay adhered to the wall of the container, and curing in a sealed container for 24 h. Adding 0.3% of EDR148, 0.3% of pentaethylenehexamine and 0.3% of the amino film forming inhibitor for the drilling fluid prepared in the embodiment 1-5, drying the mixture to constant weight after 2.0h, 4.0h and 6.0h respectively, testing XRD spectrograms of different samples by using an X-ray diffractometer to obtain grazing angles of the different samples, and calculating the clay layer spacing (the layer spacing of untreated clay is 0.9675nm) based on a Bragg equation. The calculation results are shown in table 4:

TABLE 4 Clay interlayer spacing (nm) after treatment with different inhibitors

As can be seen from Table 4, water molecules continuously intrude into the clay layers with time to cause hydration swelling. In contrast, the addition of an inhibitor is beneficial to hinder the occurrence of hydration swelling of the clay. Obviously, the effect of the amine filming inhibitor obtained in the embodiments 1 to 5 on inhibiting hydration expansion of clay is obviously better than that of EDR148 and pentaethylenehexamine, which indicates that the amine filming inhibitor for drilling fluid provided by the invention has stronger adsorption force with clay and more obvious effect on inhibiting water molecules from invading into clay layers.

Example 9

Adsorption Capacity test of amine-based film formation inhibitor

(test methods from Brookfield, Li Tao, Liu Kuang, et al. test methods for adsorption Properties of organic drilling fluid treatments [ P ]. CN 105277675A, 2014.06.26)

Adding 40 into a high-stirring cup0mL of tap water, 32g of clay and 1.6g of Na are added under a certain stirring speed₂CO₃. Stirring for 20min, stopping stirring at least twice during the stirring, scraping off clay adhered to the wall of the container, and curing in a sealed container for 24 h. And adding 0.3% of EDR148, 0.3% of pentaethylenehexamine and 0.3% of the amino film-forming inhibitor for the drilling fluid prepared in the examples 1-5, standing for 2 hours, and measuring the adsorption capacity of different samples at different temperatures by adopting a thermal filtration method. The calculation results are shown in table 5:

TABLE 5 adsorption amounts (mg/L) of different inhibitors

As can be seen from table 5, the adsorption amounts of the amine-based film formation inhibitors obtained in examples 1 to 5 are significantly higher than those of EDR148 and pentaethylenehexamine, the adsorption amount of the sample gradually decreases with the increase of temperature, and when the temperature is higher than 140 ℃, the adsorption amounts of EDR148 and pentaethylenehexamine rapidly decrease, indicating that significant desorption occurs between the sample and clay under the temperature condition; when the temperature is 160 ℃, the adsorption amount of the amino film-forming inhibitor obtained in the embodiments 1 to 5 is significantly reduced, which indicates that the temperature resistance of the amino film-forming inhibitor can reach 150 ℃.

Claims (10)

1. An amino film forming inhibitor for drilling fluid is characterized in that the structural formula of the amino film forming inhibitor is one of the following two types:

x is an integer of 0-5; y is an integer of 1-10;

wherein R is₁、R₂And R₃Is selected from-CH₃，-O-CH₃，-O-CH₂-CH₃，-o-CH₂-CH₂-O-CH₃，-O-CH₂-CH₂-O-CH₂-CH₂-O-CH₃One of them is not simultaneously selected as-CH₃。

2. An amino film-forming inhibitor for drilling fluid, which is characterized in that:

x is 0, 1, 2, 3;

y is 1, 2, 3, 4, 5.

3. A method for preparing the amine-based film-forming inhibitor for drilling fluid according to claim 1 or 2, wherein the method comprises:

fully mixing an amine compound, an alkali metal catalyst and a water removal agent in an alcohol solvent, then adding an epoxy organosilicon compound under the protection of inert gas, boosting the pressure to 0.3-0.5 MPa, reacting, filtering and distilling to obtain the amine film-forming inhibitor;

the molar ratio of the amine compound to the epoxy organosilicon organic compound is 1: 0.5-6;

the mass ratio of the alkali metal catalyst to the amine compound is 1: 500-800;

the mass ratio of the water removing agent to the amine compound is 1: 300-500.

4. The method for producing the amine-based film formation inhibitor according to claim 3, wherein:

the reaction temperature is 70-120 ℃; the reaction time is 1-5 h.

5. The method for producing the amine-based film formation inhibitor according to claim 4, wherein:

the reaction temperature is 90-110 ℃.

6. The method for producing the amine-based film formation inhibitor according to claim 3, wherein:

the alkali metal catalyst is one of NaOH and KOH;

the alcohol solvent is one of methanol and ethanol;

the water removing agent is anhydrous CaCl₂。

7. The method for producing the amine-based film formation inhibitor according to claim 3, wherein:

the molar ratio of the amine compound to the epoxy organosilicon organic compound is 1: 1-3;

the mass ratio of the alkali metal catalyst to the amine compound is 1: 500-600;

the mass ratio of the water removing agent to the amine compound is 1: 300-400.

8. The method for producing the amine-based film formation inhibitor according to claim 3, wherein:

the mass percentage concentration of the amine compound in the alcohol solvent is 5.0-20%.

9. The method for producing the amine-based film formation inhibitor according to claim 3, wherein:

the structural formula of the amine compound is as follows:

x is an integer of 0-5, and y is an integer of 1-10;

the structural formula of the epoxy organosilicon compound is as follows:

wherein R is₁、R₂And R₃Is selected from-CH₃，-O-CH₃，-O-CH₂-CH₃，-o-CH₂-CH₂-O-CH₃，-O-CH₂-CH₂-O-CH₂-CH₂-O-CH₃One of them is not simultaneously selected as-CH₃。

10. The method for producing the amine-based film formation inhibitor according to claim 9, wherein:

x is 0, 1, 2, 3;

y is 1, 2, 3, 4, 5.

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