CN115820226A - Wetting reversal agent and preparation method and application thereof - Google Patents

Abstract

The invention relates to the technical field of wetting reversal agents for drilling fluids, and provides a wetting reversal agent and a preparation method and application thereof. The wetting reversal agent is prepared from fatty acid, organic amine, a quaternizing agent and a diluent according to the mass-volume ratio of 1.8-2.2 g: 0.8-1.2 g: 0.8-1.2 g: 0.2-0.4 mL. The preparation method is simple and convenient, the cost is low, the obtained wetting reversal agent is uniformly mixed with diesel oil, then the barite is added, the oil phase precipitation rate is 28-30% after 12h standing, the gelling rate is 70-72%, and no obvious settlement of the barite occurs. In the oil-based drilling fluid, the wetting reversal agent and the surface of the weighting material form an effective adsorption effect, the hydrophilic property of the surface of the weighting material is changed, the compatibility of the weighting material and an oil-based drilling fluid system is improved, and the problem of the sedimentation stability of the weighting material in the system is solved.

Description

A wetting reversal agent and its preparation method and application

technical field

The invention relates to the technical field of wetting reversal agent for drilling fluid, in particular to a wetting reversal agent and its preparation method and application.

Background technique

With the gradual increase of drilling depth, there are more and more extended-reach wells and horizontal wells, and the requirements for drilling fluid in the process of oil and gas drilling and production are also getting higher and higher. Oil-based drilling fluids are widely used because of their excellent temperature resistance, stability and inhibition. However, in the process of continuous application and research, it was found that with the increase of oil-based drilling fluid density, the system subsidence became more and more serious, and the reason was analyzed to be related to the weighting materials in oil-based drilling fluid. At present, the weighting materials used in both water-based drilling fluids and oil-based drilling fluids are natural inert solid particles such as barite. These natural materials with a hydrophilic surface have extremely low compatibility with oil-based drilling fluids , when added to oil-based drilling fluid, it is prone to coalescence and settlement. As the density of oil-based drilling fluid increases, the mass of the weighting material required in the system increases, so the possibility of coalescence among the solid particles of each weighting material increases, resulting in more serious settlement problems in oil-based drilling fluid. Therefore, it is of great significance to provide an additive to weaken the coalescence and settlement of the weighted material in the oil-based drilling fluid system.

Contents of the invention

The purpose of the present invention is to overcome the problems existing in the prior art, and provide a wetting reversal agent and its preparation method and application.

In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:

The invention provides a wetting reversal agent, which is prepared from raw materials comprising the following ratios:

Fatty acids, organic amines, quaternizing agents and diluents;

The mass volume ratio of the fatty acid, the organic amine, the quaternizing agent and the diluent is 1.8-2.2g: 0.8-1.2g: 0.8-1.2g: 0.2-0.4mL.

Preferably, the fatty acid is one or more of lauric acid, palmitic acid and oleic acid; the organic amine is diethylenetriamine, triethylenetetramine, tetraethylenepentamine and hydroxyethylethylenediamine one or more of .

Preferably, the quaternizing agent is one or more of benzyl chloride, ethyl chloroacetate, sodium chloroacetate and chloroacetic acid; the diluent is n-butanol, ethylene glycol methyl ether and propylene glycol methyl One or more of ethers.

The present invention also provides a preparation method of the wetting reversal agent, comprising the following steps:

(1) In a protective atmosphere, the fatty acid is mixed with an organic amine and then reacted to obtain an intermediate product;

(2) carry out quaternization reaction after intermediate product is mixed with quaternization reagent, obtain quaternization product;

(3) Mixing the quaternization product with a diluent to obtain the wetting reversal agent.

Preferably, the mixing speed in step (1) is 600-1000 rpm, the mixing time is 1.5-2.5 hours, and the mixing temperature is 45-55°C.

Preferably, the reaction described in step (1) is an initial reaction and a cyclization reaction carried out in sequence;

The temperature of the initial reaction is 100-140° C., and the time of the initial reaction is 4-6 hours;

The temperature of the cyclization reaction is 180-220° C., and the time of the cyclization reaction is 3-5 hours;

The heating rate from the mixing temperature to the initial reaction temperature is 1-4°C/min; the heating rate from the initial reaction temperature to the cyclization reaction temperature is 2-6°C/min.

Preferably, the temperature of the quaternization reaction in step (2) is 80-120° C., and the time of the quaternization reaction is 3-5 hours.

Preferably, the mixing temperature in step (3) is 20-40° C., the mixing speed is 400-600 rpm, and the mixing time is 0.5-1.5 h.

The invention also provides the application of the wettability reversal agent in oil-based drilling fluid.

The beneficial effects of the present invention are:

(1) The invention provides a preparation method of a wetting reversal agent, comprising the following steps: in a protective atmosphere, reacting an intermediate product after mixing the fatty acid with an organic amine; mixing the intermediate product with a quaternizing agent The quaternization reaction is carried out to obtain a quaternization product; the quaternization product is mixed with a diluent to obtain the wetting reversal agent. The preparation method provided by the invention is simple and low in cost. The obtained wetting reversal agent has excellent thermal stability and obvious application effect. In oil-based drilling fluid, it forms an interaction with the surface of the weighting material mainly by physical adsorption and supplemented by chemical adsorption. The function changes the hydrophilic property of the surface of the weighted material, increases the compatibility between the weighted material and the oil-based drilling fluid system, and solves the problem of the settlement stability of the weighted material in the oil-based system.

(2) After the wetting reversal agent provided by the present invention is mixed with diesel oil evenly, barite is added, and the oil phase precipitation rate is 28-30% after standing for 12 hours, and the gelation rate is 70-72%. Significant subsidence occurred.

Detailed ways

The invention provides a wetting reversal agent, which is prepared from raw materials comprising the following ratios:

Fatty acids, organic amines, quaternizing agents and diluents;

The mass volume ratio of the fatty acid, organic amine, quaternizing agent and diluent is 1.8-2.2g: 0.8-1.2g: 0.8-1.2g: 0.2-0.4mL, preferably 1.9-2.1g: 0.9-1.1g : 0.9-1.1g: 0.25-0.35mL, more preferably 1.95-2.05g: 0.95-1.05g: 0.95-1.05g: 0.27-0.33mL.

In the present invention, the fatty acid is one or more of lauric acid, palmitic acid and oleic acid; the organic amine is diethylenetriamine, triethylenetetramine, tetraethylenepentamine and hydroxyethylethylenediamine One or more of amines.

In the present invention, the quaternization reagent is one or more of benzyl chloride, ethyl chloroacetate, sodium chloroacetate and chloroacetic acid; the diluent is n-butanol, ethylene glycol methyl ether and One or more of propylene glycol methyl ether.

The present invention also provides a preparation method of the wetting reversal agent, comprising the following steps:

(1) In a protective atmosphere, the fatty acid is mixed with an organic amine and then reacted to obtain an intermediate product;

(2) carry out quaternization reaction after intermediate product is mixed with quaternization reagent, obtain quaternization product;

(3) Mixing the quaternization product with a diluent to obtain the wetting reversal agent.

In the present invention, if the fatty acid is a solid fatty acid, it is necessary to heat the solid fatty acid under stirring until it is completely melted, and then mix it with the organic amine.

In the present invention, the protective atmosphere is preferably nitrogen, helium or neon.

In the present invention, the heating temperature is preferably 45-55°C, more preferably 48-52°C, more preferably 49-51°C; the stirring speed is preferably 500-700rpm, more preferably 550-650rpm , more preferably 580 to 620 rpm.

In the present invention, the mixing speed in step (1) is preferably 600-1000rpm, more preferably 700-900rpm, more preferably 750-850rpm; the mixing time is preferably 1.5-2.5h, more preferably 1.7 ~2.3h, more preferably 1.9~2.1h; the mixing temperature is preferably 45~55°C, more preferably 48~52°C, more preferably 49~51°C.

In the present invention, the reaction described in step (1) is an initial reaction and a cyclization reaction carried out in sequence;

The temperature of the initial reaction is preferably 100-140°C, more preferably 110-130°C, more preferably 115-125°C; the initial reaction time is preferably 4-6h, more preferably 4.5-5.5h, more preferably Preferably 4.7～5.2h;

The temperature of the cyclization reaction is preferably 180-220°C, more preferably 190-210°C, more preferably 195-205°C; the time of the cyclization reaction is preferably 3-5h, more preferably 3.5-4.5h , more preferably 3.7～4.2h;

The heating rate from the mixing temperature to the initial reaction temperature is preferably 1-4°C/min, more preferably 1.5-3.5°C/min, more preferably 2-3°C/min; from the initial reaction temperature to the cyclization reaction The temperature increase rate is preferably 2 to 6°C/min, more preferably 3 to 5°C/min, more preferably 3.5 to 4.5°C/min.

In the present invention, silicone oil is used to heat up the reaction. The specific heat capacity of silicone oil is 2.49KJ/(Kg°C) at 20°C, and 1.63KJ/(Kg°C) at 100°C. The temperature increase rate to the initial reaction temperature is lower than the temperature increase rate from the initial reaction temperature to the cyclization reaction temperature.

In the present invention, when the cyclization reaction is terminated, the system is anhydrous. At this time, the system is naturally cooled, cooled to the temperature of the quaternization reaction and kept constant, and the quaternization reagent is added.

In the present invention, the temperature of the quaternization reaction in step (2) is preferably 80-120°C, more preferably 90-110°C, more preferably 95-105°C; the time of the quaternization reaction is preferably 3 to 5 hours, more preferably 3.5 to 4.5 hours, more preferably 3.7 to 4.2 hours.

In the present invention, when the quaternization reaction is finished, the system is cooled naturally, cooled to the temperature mixed in step (3) and kept constant, and the diluent is added.

In the present invention, the mixing temperature in step (3) is preferably 20-40°C, more preferably 25-35°C, more preferably 27-33°C; the mixing speed is preferably 400-600rpm, more preferably 450-550 rpm, more preferably 470-520 rpm; the mixing time is preferably 0.5-1.5 h, more preferably 0.6-1.4 h, more preferably 0.8-1.2 h.

The invention also provides the application of the wettability reversal agent in oil-based drilling fluid.

The technical solutions provided by the present invention will be described in detail below in conjunction with the examples, but they should not be interpreted as limiting the protection scope of the present invention.

Example 1

Add 20g of solid lauric acid into a four-neck flask, heat and stir at 50°C at a speed of 600rpm until completely melted, then add 10g of diethylenetriamine under a nitrogen atmosphere, mix for 2 hours at a speed of 800rpm, and stop after mixing Introduce nitrogen, raise the temperature of the oil bath to 120°C at a rate of 3°C/min for the initial reaction for 5 hours, and then raise the temperature to 200°C at a rate of 4°C/min for cyclization for 4 hours after the initial reaction. Naturally cool the pot to 100°C, add 10g of benzyl chloride to the four-necked flask to react for 4 hours, after the quaternization reaction, cool the oil bath pot naturally again, lower the temperature to 30°C, add 3mL of n-butanol to the four-necked flask , and stirred for 1 h at a speed of 500 rpm to obtain the wetting reversal agent.

Weigh 1.5g of the wetting reversal agent prepared in this example and add it to a high stirring cup, then add 100mL of 0# diesel oil, stir for 5min at a speed of 8000rpm to completely dissolve the wetting reversal agent, then add 20g of API barite , and continued to stir for 10 minutes. After the end, pour the sample into a 100mL graduated cylinder and let it stand for 12 hours. At the same time, the comparative example of this embodiment is set, and other conditions are kept unchanged, and the step of adding the wetting reversal agent in this embodiment is omitted. The experimental results show that the barite completely settles after 12 hours of standing for the test sample without the wetting reversal agent, and the oil phase precipitation rate of the test sample with the addition of the wetness reversal agent is 30% after standing for 12 hours, and the gelation rate 70%, barite did not significantly settle.

Example 2

Add 19g of solid palmitic acid into a four-necked flask, heat and stir at 48°C at a speed of 700rpm until completely melted, then add 9g of triethylenetetramine under a helium atmosphere, mix for 2.2h at a speed of 700rpm, and the mixing is completed Then stop feeding helium, and raise the temperature of the oil bath to 110°C at a rate of 2°C/min for the initial reaction for 5.5 hours. After the initial reaction, raise the temperature to 195°C at a rate of 3°C/min for cyclization reaction 4.2 h, naturally cool the oil bath to 90°C, add 8.5g of ethyl chloroacetate to the four-neck flask and react for 4.6h, after the quaternization reaction, cool the oil bath naturally again, lower the temperature to 25°C, Add 2.6 mL of ethylene glycol methyl ether into the flask, and stir at 450 rpm for 1.3 h to obtain the wetting reversal agent.

Weigh 1.5g of the wetting reversal agent prepared in this example and add it to a high stirring cup, then add 100mL of 0# diesel oil, stir for 5min at a speed of 8000rpm to completely dissolve the wetting reversal agent, then add 20g of API barite , and continued to stir for 10 minutes. After the end, pour the sample into a 100mL graduated cylinder and let it stand for 12 hours. At the same time, the comparative example of this embodiment is set, and other conditions are kept unchanged, and the step of adding the wetting reversal agent in this embodiment is omitted. The experimental results show that the barite completely settles after 12 hours of standing for the test sample without the wetting inversion agent, and the oil phase precipitation rate of the test sample with the wetting inversion agent is 29% after standing for 12 hours, and the gelation rate 71%, barite did not significantly settle.

Example 3

Add 22g of liquid oleic acid into a four-neck flask, add 11.5g of hydroxyethylethylenediamine under a neon gas atmosphere with a rotation speed of 550rpm and a temperature of 54°C, and mix at a rotation speed of 900rpm for 1.7h. Stop feeding the neon gas, raise the temperature of the oil bath to 135°C at a rate of 3.5°C/min for initial reaction for 4.2 hours, and then raise the temperature to 205°C at a rate of 5°C/min for cyclization reaction for 3.8 hours after the initial reaction , naturally cool the oil bath to 110°C, add 12g of chloroacetic acid to the four-necked flask to react for 3.6h, after the quaternization reaction, cool the oil bath naturally again, lower the temperature to 32°C, add to the four-necked flask 3.8 mL of propylene glycol methyl ether was stirred at 600 rpm for 0.9 h to obtain the wetting reversal agent.

Weigh 1.5g of the wetting reversal agent prepared in this example and add it to a high stirring cup, then add 100mL of 0# diesel oil, stir for 5min at a speed of 8000rpm to completely dissolve the wetting reversal agent, then add 20g of API barite , and continued to stir for 10 minutes. After the end, pour the sample into a 100mL graduated cylinder and let it stand for 12 hours. At the same time, the comparative example of this embodiment is set, and other conditions are kept unchanged, and the step of adding the wetting reversal agent in this embodiment is omitted. The experimental results show that the barite completely settles after 12 hours of standing for the test sample without the wetting inversion agent, and the oil phase precipitation rate of the test sample with the wetting inversion agent is 28% after standing for 12 hours, and the gelation rate 72%, no significant settlement of barite occurred.

It can be known from the above examples that after the wetting reversal agent provided by the present invention is uniformly mixed with diesel oil, barite is added, and after standing for 12 hours, the oil phase precipitation rate is 28-30%, and the gelation rate is 70-72%. There is no obvious settlement phenomenon of barite; the wetting reversal agent provided by the present invention has excellent thermal stability and obvious application effect. In oil-based drilling fluid, it forms an interaction with the surface of the weighting material mainly by physical adsorption and supplemented by chemical adsorption. The function changes the hydrophilic property of the surface of the weighted material, increases the compatibility between the weighted material and the oil-based drilling fluid system, and solves the problem of the settlement stability of the weighted material in the oil-based system.

The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.

Claims (9)

1. A wetting reversal agent, characterized in that it is prepared from raw materials comprising the following ratios: Fatty acids, organic amines, quaternizing agents and diluents; The mass volume ratio of the fatty acid, the organic amine, the quaternizing agent and the diluent is 1.8-2.2g: 0.8-1.2g: 0.8-1.2g: 0.2-0.4mL. 2. wetness inversion agent as claimed in claim 1 is characterized in that, described fatty acid is one or more in lauric acid, palmitic acid and oleic acid; One or more of ethylene tetramine, tetraethylene pentamine and hydroxyethyl ethylene diamine. 3. Wetting reversal agent as claimed in claim 1 or 2, is characterized in that, described quaternization reagent is one or more in benzyl chloride, ethyl chloroacetate, sodium chloroacetate and chloroacetic acid ; The diluent is one or more of n-butanol, ethylene glycol methyl ether and propylene glycol methyl ether. 4. The preparation method of the wetting reversal agent described in any one of claims 1 to 3, characterized in that it comprises the following steps: (1) In a protective atmosphere, the fatty acid is mixed with an organic amine and then reacted to obtain an intermediate product; (2) carry out quaternization reaction after intermediate product is mixed with quaternization reagent, obtain quaternization product; (3) Mixing the quaternization product with a diluent to obtain the wetting reversal agent. 5. The preparation method according to claim 4, characterized in that the mixing speed in step (1) is 600-1000 rpm, the mixing time is 1.5-2.5 hours, and the mixing temperature is 45-55 ℃. 6. preparation method as claimed in claim 5 is characterized in that, step (1) described reaction is initial reaction and cyclization reaction carried out in sequence; The temperature of the initial reaction is 100-140° C., and the time of the initial reaction is 4-6 hours; The temperature of the cyclization reaction is 180-220° C., and the time of the cyclization reaction is 3-5 hours; The heating rate from the mixing temperature to the initial reaction temperature is 1-4°C/min; the heating rate from the initial reaction temperature to the cyclization reaction temperature is 2-6°C/min. 7. The preparation method according to claim 5 or 6, characterized in that the temperature of the quaternization reaction in step (2) is 80-120° C., and the time of the quaternization reaction is 3-5 hours. 8. The preparation method according to claim 7, characterized in that the mixing temperature in step (3) is 20-40° C., the mixing speed is 400-600 rpm, and the mixing time is 0.5-1.5 h. 9. The application of the wettability reversal agent according to any one of claims 1 to 3 in oil-based drilling fluid.