CN115417832B

CN115417832B - High-resistance Wen Danyou lubricant and preparation method thereof

Info

Publication number: CN115417832B
Application number: CN202211244793.2A
Authority: CN
Inventors: 吴瑛莹
Original assignee: Locks Oil Zhejiang Co ltd
Current assignee: Locks Oil Zhejiang Co ltd
Priority date: 2022-10-12
Filing date: 2022-10-12
Publication date: 2023-05-02
Anticipated expiration: 2042-10-12
Also published as: CN115417832A

Abstract

The invention relates to a high-resistance Wen Danyou lubricant and a preparation method thereof, belonging to the technical field of petrochemical industry. The lubricant takes 2-mercapto-6-nitrobenzothiazole containing sulfur-nitrogen heterocycle as a functional raw material, and is prepared into an esterified substance containing branch sulfur-nitrogen heterocycle by adding and grafting carboxyl to acrylic acid and esterifying with pentaerythritol, and the esterified substance and a drill rod matrix generate multi-site anchoring action, so that the adsorption strength of a lubricating film is enhanced, and the lubricating film is not easy to fall off and lose efficacy under the working conditions of high load pressure and high friction heat, thereby achieving the effect of heat-resistant lubrication; and then reducing nitro into amino, and introducing sulfonic acid groups with strong hydrophilicity to the end parts through chlorosulfonic acid and substitution modification, so that the lubricant has good water solubility, can be used as an additive of water-based drilling fluid, and is more environment-friendly.

Description

High-resistance Wen Danyou lubricant and preparation method thereof

Technical Field

The invention belongs to the technical field of petrochemical industry, and particularly relates to a high-resistance Wen Danyou lubricant and a preparation method thereof.

Background

Friction damage is a physical injury that cannot be completely avoided in oil and gas drilling development activities. The lubricating property of the drilling fluid is improved by adding the lubricant, the friction between the well wall and the drilling tool is reduced, the drilling efficiency can be effectively improved, and the accident rate is reduced.

The traditional lubricant is selected from mineral oil such as crude oil, engine oil, diesel oil and the like, and oil content of the mineral oil contains a large amount of high-viscosity colloid, so that an oil film can be formed between a drilling tool and a rock wall, and certain stability is maintained, but the mineral oil is difficult to naturally decompose, has potential safety hazards, and has large performance change along with temperature and is gradually replaced.

In the prior art, the synthetic ester is adopted to replace mineral oil, so that the negative influence that the mineral oil and asphalt products used in the past are difficult to biodegrade and have serious pollution to the environment is changed, the waste treatment cost of drilling fluid can be greatly reduced, and the adverse influence of the waste drilling fluid on the environment is relieved. However, a large amount of heat is generated in the drilling process, the rheological properties of the existing synthetic ester are greatly different in a high-heat environment, and a stable lubricating film is difficult to form between a drill rod and a rock wall; accordingly, the present application aims to develop a lubricant that maintains stable lubrication under high heat conditions.

Disclosure of Invention

In order to solve the technical problems mentioned in the background art, the invention aims to provide a high Wen Danyou resistant lubricant and a preparation method thereof.

The aim of the invention can be achieved by the following technical scheme:

the preparation method of the high Wen Danyou resistant lubricant specifically comprises the following steps:

step A1: mixing 2-mercapto-6-nitrobenzothiazole, acrylic acid and DMF, heating, stirring and dissolving, adding 2, 2-dimethylolpropionic acid, heating to 90-100 ℃, stirring and reacting for 3-4 hours under ultraviolet irradiation, and carrying out addition reaction on the 2-mercapto-6-nitrobenzothiazole and the acrylic acid under the catalysis of the 2, 2-dimethylolpropionic acid and ultraviolet initiation to prepare a carboxylated intermediate;

further, the ratio of the amount of 2-mercapto-6-nitrobenzothiazole, acrylic acid, DMF and 2, 2-dimethylolpropionic acid was 0.1mol:0.1mol:30-40mL:0.2-0.3g, and the ultraviolet light is near ultraviolet light.

The specific reaction process is as follows:

step A2: mixing dioxane and water as a solvent, adding a carboxylation intermediate and pentaerythritol, stirring for dissolution, then adding p-toluenesulfonic acid, heating to 100-106 ℃ for reflux reaction for 2-3h, and carrying out esterification reaction on the carboxylation intermediate and pentaerythritol to obtain a branched esterified substance;

further, the ratio of carboxylated intermediate, pentaerythritol, toluene sulfonic acid, dioxane and water was 0.4mol:0.1mol:0.1-0.15g:50-100mL:80-150mL.

The specific reaction process is as follows:

step A3: dissolving sodium sulfide and sodium thiosulfate in DMF water solution under the protection of nitrogen, adding the branched esterified substance, mixing and heating to 60 ℃, stirring and reducing for 3 hours, wherein nitro in the branched esterified substance is reduced into amino, and preparing an aminated esterified substance;

further, the ratio of the amount of the branched esterified substance, sodium sulfide, sodium thiosulfate and DMF aqueous solution was 100g:1.3-1.5g:0.5-0.8g:220mL.

The specific reaction process is as follows:

step A4: mixing the amination esterified substance and absolute ethyl alcohol under the protection of nitrogen, heating to 40-50 ℃, setting the stirring speed to 600rpm, dripping chlorosulfonic acid, stirring and reacting for 20min, adding water for mixing after the reaction, and performing rotary evaporation under reduced pressure to obtain the high Wen Danyou-resistant lubricant;

further, the ratio of the amount of the aminated ester, chlorosulfonic acid and absolute ethanol was 100g:0.4mol:260mL.

The specific reaction process is as follows:

the invention has the beneficial effects that:

1. the invention takes the sulfur-nitrogen heterocycle-containing 2-mercapto-6-nitrobenzothiazole as a functional raw material, has high electronegativity of the nitrogen-containing heterocycle structure, is easy to form hydrogen bonds among molecules, improves the strength of a lubricating film, and is easy to form iron sulfide with low shearing strength with the metal surface to enhance the lubricity, thereby having good lubricating effect.

2. According to the invention, acrylic acid reacts with 2-mercapto-6-nitrobenzothiazole, carboxyl is grafted, and then the acrylic acid is esterified with pentaerythritol to prepare the esterification product containing branched thiazate, on one hand, the esterification product has a certain lubricating effect and plays a role in auxiliary lubrication, on the other hand, the branched thiazate and a drill rod base body generate a multi-site anchoring effect, so that the adsorption strength of a lubricating film is enhanced, and the lubricating film is not easy to fall off and lose efficacy under the working conditions of high load pressure and high friction heat, thereby the high-temperature resistant characteristic is shown.

3. The lubricant has ingenious molecular structure design, is reserved at the end, is reduced into amino through sodium sulfide and sodium thiosulfate, is substituted by chlorosulfonic acid, and is introduced with a sulfonic acid group with strong hydrophilicity, so that the lubricant has good water solubility, can be used as an additive of water-based drilling fluid, and is more environment-friendly.

Detailed Description

The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.

Example 1

The preparation method of the high-temperature-resistant petroleum lubricant comprises the following specific implementation processes:

a1, adding 2-mercapto-6-nitrobenzothiazole, acrylic acid and DMF into a reaction kettle, mixing, preheating to 50 ℃ for stirring and dissolving, then adding 2, 2-dimethylolpropionic acid, setting the stirring speed to 240rpm, heating to 90 ℃, applying near ultraviolet light irradiation, wherein the irradiation distance is 20cm, the irradiation reaction time is 4 hours, adding methanol for decompression, rotary steaming and purifying after the reaction is finished to obtain a carboxylated intermediate, wherein the dosage ratio of the 2-mercapto-6-nitrobenzothiazole to the acrylic acid to the DMF to the 2, 2-dimethylolpropionic acid is 0.1mol:0.1mol:30mL:0.2g.

A2, adding dioxane and water into a reaction kettle, stirring and mixing the mixture to serve as a solvent, adding a carboxylated intermediate and pentaerythritol, stirring and dissolving the mixture, adding p-toluenesulfonic acid, heating to 100 ℃, refluxing for 3 hours, and removing the solvent after the reaction is finished by rotary evaporation to obtain a branched esterified substance, wherein in the reaction, the dosage ratio of the carboxylated intermediate, pentaerythritol, toluenesulfonic acid, dioxane and water is 0.4mol:0.1mol:0.1g:50mL:150mL.

a3, introducing nitrogen into the reaction kettle for protection, adding sodium sulfide, sodium thiosulfate and 80% DMF aqueous solution, stirring and dissolving, adding the branched esterified substance, mixing and heating to 60 ℃, stirring and reducing for 3 hours, washing and separating liquid after the reaction is finished, and drying with nitrogen to obtain the aminated esterified substance, wherein in the reaction, the dosage ratio of the branched esterified substance, the sodium sulfide, the sodium thiosulfate and the DMF aqueous solution is 100g:1.3g:0.8g:220mL.

a4, introducing nitrogen into the reaction kettle for protection, mixing the amination esterified substance and the absolute ethyl alcohol, heating to 40 ℃, controlling the stirring speed to 600rpm, dropwise adding chlorosulfonic acid, controlling the dropwise adding speed to 10mL/min, continuously stirring for 20min after dropwise adding, adding water with the volume of 1/5 of the reaction liquid for stirring and mixing after reaction, and then performing reduced pressure rotary evaporation to remove water and ethanol to obtain the high Wen Danyou resistant lubricant, wherein in the reaction, the dosage ratio of the amination esterified substance, the chlorosulfonic acid and the absolute ethyl alcohol is 100g:0.4mol:260mL.

Example 2

a1, adding 2-mercapto-6-nitrobenzothiazole, acrylic acid and DMF into a reaction kettle, mixing, preheating to 50 ℃ for stirring and dissolving, then adding 2, 2-dimethylolpropionic acid, setting the stirring speed to 240rpm, heating to 100 ℃, applying near ultraviolet light irradiation, wherein the irradiation distance is 20cm, the irradiation reaction time is 3h, adding methanol for decompression, rotary steaming and purifying after the reaction is finished, and obtaining carboxylated intermediate, wherein the dosage ratio of 2-mercapto-6-nitrobenzothiazole, acrylic acid, DMF and 2, 2-dimethylolpropionic acid is 0.1mol:0.1mol:40mL:0.3g.

A2, adding dioxane and water into a reaction kettle, stirring and mixing the mixture to serve as a solvent, adding a carboxylated intermediate and pentaerythritol, stirring and dissolving the mixture, adding p-toluenesulfonic acid, heating to 106 ℃ and refluxing the mixture for 2 hours, and removing the solvent after the reaction is finished by rotary evaporation to obtain a branched esterified substance, wherein in the reaction, the dosage ratio of the carboxylated intermediate, pentaerythritol, toluenesulfonic acid, dioxane and water is 0.4mol:0.1mol:0.15g:100mL:80mL.

a3, introducing nitrogen into the reaction kettle for protection, adding sodium sulfide, sodium thiosulfate and 80% DMF aqueous solution, stirring and dissolving, adding the branched esterified substance, mixing and heating to 60 ℃, stirring and reducing for 3 hours, washing and separating liquid after the reaction is finished, and drying with nitrogen to obtain the aminated esterified substance, wherein in the reaction, the dosage ratio of the branched esterified substance, the sodium sulfide, the sodium thiosulfate and the DMF aqueous solution is 100g:1.5g:0.5g:220mL.

a4, introducing nitrogen into the reaction kettle for protection, mixing the amination esterified substance and the absolute ethyl alcohol, heating to 50 ℃, controlling the stirring speed to 600rpm, dropwise adding chlorosulfonic acid, controlling the dropwise adding speed to 10mL/min, continuously stirring for 20min after dropwise adding, adding water with the volume of 1/5 of the reaction liquid for stirring and mixing after reaction, and then performing reduced pressure rotary evaporation to remove water and ethanol to obtain the high Wen Danyou resistant lubricant, wherein in the reaction, the dosage ratio of the amination esterified substance, the chlorosulfonic acid and the absolute ethyl alcohol is 100g:0.4mol:260mL.

Example 3

a1, adding 2-mercapto-6-nitrobenzothiazole, acrylic acid and DMF into a reaction kettle, mixing, preheating to 50 ℃ for stirring and dissolving, then adding 2, 2-dimethylolpropionic acid, setting the stirring speed to 240rpm, heating to 95 ℃, applying near ultraviolet light irradiation, wherein the irradiation distance is 20cm, the irradiation reaction time is 3.3h, adding methanol for decompression rotary evaporation and purification after the reaction is finished, and obtaining carboxylated intermediate, wherein the dosage ratio of 2-mercapto-6-nitrobenzothiazole, acrylic acid, DMF and 2, 2-dimethylolpropionic acid is 0.1mol:0.1mol:38mL:0.26g.

A2, adding dioxane and water into a reaction kettle, stirring and mixing the mixture to serve as a solvent, adding a carboxylated intermediate and pentaerythritol, stirring and dissolving the mixture, adding p-toluenesulfonic acid, heating to 105 ℃ and refluxing for 2.8 hours, and removing the solvent after the reaction is finished by rotary evaporation to obtain a branched esterified substance, wherein in the reaction, the dosage ratio of the carboxylated intermediate, pentaerythritol, toluenesulfonic acid, dioxane and water is 0.4mol:0.1mol:0.13g:80mL:100mL.

a3, introducing nitrogen into the reaction kettle for protection, adding sodium sulfide, sodium thiosulfate and 80% DMF aqueous solution, stirring and dissolving, adding the branched esterified substance, mixing and heating to 60 ℃, stirring and reducing for 3 hours, washing and separating liquid after the reaction is finished, and drying with nitrogen to obtain the aminated esterified substance, wherein in the reaction, the dosage ratio of the branched esterified substance, the sodium sulfide, the sodium thiosulfate and the DMF aqueous solution is 100g:1.4g:0.7g:220mL.

a4, introducing nitrogen into the reaction kettle for protection, mixing the amination esterified substance and the absolute ethyl alcohol, heating to 40-50 ℃, controlling the stirring speed to 600rpm, dropwise adding chlorosulfonic acid, controlling the dropwise adding speed to 10mL/min, continuously stirring for 20min after dropwise adding, adding water with the volume of 1/5 of the reaction liquid for stirring and mixing after reaction, and removing water and the ethanol by reduced pressure rotary evaporation to obtain the high Wen Danyou resistant lubricant, wherein in the reaction, the dosage ratio of the amination esterified substance, the chlorosulfonic acid and the absolute ethyl alcohol is 100g:0.4mol:260mL.

Example 4

a1, adding 2-mercapto-6-nitrobenzothiazole, acrylic acid and DMF into a reaction kettle, mixing, preheating to 50 ℃ for stirring and dissolving, then adding 2, 2-dimethylolpropionic acid, setting the stirring speed to 240rpm, heating to 106 ℃, applying near ultraviolet light irradiation, wherein the irradiation distance is 20cm, the irradiation reaction time is 3.6h, adding methanol for decompression rotary evaporation and purification after the reaction is finished, and obtaining carboxylated intermediate, wherein the dosage ratio of 2-mercapto-6-nitrobenzothiazole, acrylic acid, DMF and 2, 2-dimethylolpropionic acid is 0.1mol:0.1mol:35mL:0.28g.

A2, adding dioxane and water into a reaction kettle, stirring and mixing the mixture to serve as a solvent, adding a carboxylated intermediate and pentaerythritol, stirring and dissolving the mixture, adding p-toluenesulfonic acid, heating to 104 ℃ and refluxing for 2.5 hours, and removing the solvent after the reaction is finished by rotary evaporation to obtain a branched esterified substance, wherein in the reaction, the dosage ratio of the carboxylated intermediate, pentaerythritol, toluenesulfonic acid, dioxane and water is 0.4mol:0.1mol:0.15g:90mL:110mL.

a3, introducing nitrogen into the reaction kettle for protection, adding sodium sulfide, sodium thiosulfate and 80% DMF aqueous solution, stirring and dissolving, adding the branched esterified substance, mixing and heating to 60 ℃, stirring and reducing for 3 hours, washing and separating liquid after the reaction is finished, and drying with nitrogen to obtain the aminated esterified substance, wherein in the reaction, the dosage ratio of the branched esterified substance, the sodium sulfide, the sodium thiosulfate and the DMF aqueous solution is 100g:1.4g:0.6g:220mL.

In order to verify the performance of the high-temperature-resistant petroleum lubricant prepared above, the high-temperature-resistant petroleum lubricant is compounded with common raw materials to form drilling fluid, and the actual use state is simulated, and the specific operation is as follows:

the weight portions are as follows:

22 parts of regenerated engine oil as base oil

10 parts of the high-temperature-resistant petroleum lubricant prepared in the example

3 parts of sodium dodecylbenzenesulfonate as surfactant

5 parts of emulsifier OP-10 as emulsifier

2 parts of sodium carboxymethylcellulose as stabilizer

1 part of sodium nitrite as antirust agent

57 parts of water as diluent

The raw materials are added into a high-speed mixing kettle, stirred and mixed for 10min at a high speed of 1800rpm, and then the emulsion-shaped drilling fluid is prepared.

Comparative example 1

The comparative example was formulated with the high Wen Danyou lubricant replaced with the same parts by weight base oil.

The drilling fluid compounded by the above is tested by referring to Q/SY17088-2016, and the specific test results are shown in Table 1:

TABLE 1

As can be seen from the data in table 1, the lubricant prepared by the present invention satisfies the use standard of the lubricant for drilling fluid, wherein the reduction rate of the lubrication coefficient reaches 91.47-93.65%, and exhibits excellent lubrication performance.

The drilling fluids compounded by the above are respectively subjected to temperature resistance test at 100 ℃, 120 ℃, 140 ℃ and 160 ℃, and specific test results are shown in table 2:

TABLE 2

As can be seen from the data in Table 2, the lubricant prepared by the invention has smaller rheological property and coefficient of friction change rate along with the temperature rise, and maintains stable lubrication effect.

The drilling fluid compounded by the above is respectively subjected to extreme pressure film strength test at 100 ℃, 120 ℃, 140 ℃ and 160 ℃, and specific test data are shown in table 3:

TABLE 3 Table 3

As can be seen from the data in Table 3, the strength of the lubricating film of the drilling fluid is remarkably improved by adding the lubricant prepared by the invention, and the lubricating film still maintains high strength at 100-160 ℃ and maintains stable lubricating effect.

In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.

Claims

1. The preparation method of the high-temperature-resistant Wen Danyou lubricant is characterized by comprising the following steps of:

the preparation method comprises the following steps:

step A1: mixing 2-mercapto-6-nitrobenzothiazole, acrylic acid and DMF, heating to dissolve, adding 2, 2-dimethylolpropionic acid, heating to 90-100 ℃, and stirring for reaction for 3-4h under ultraviolet irradiation to obtain a carboxylated intermediate;

step A2: mixing dioxane and water, adding carboxylated intermediate and pentaerythritol, stirring for dissolution, adding p-toluenesulfonic acid, heating to 100-106 ℃ for reflux reaction for 2-3h, and obtaining branched esterified substance;

step A3: dissolving sodium sulfide and sodium thiosulfate in DMF water solution under the protection of nitrogen, adding the branched esterified substance, mixing, heating to 60 ℃, stirring and reducing for 3 hours to obtain an aminated esterified substance;

step A4: mixing the amination esterified substance and absolute ethyl alcohol under the protection of nitrogen, heating to 40-50 ℃, setting the stirring speed to 600rpm, dripping chlorosulfonic acid, stirring and reacting for 20min, adding water for mixing after the reaction, and performing rotary evaporation under reduced pressure to obtain the high Wen Danyou-resistant lubricant.

2. The method for preparing the high Wen Danyou resistant lubricant according to claim 1, wherein the dosage ratio of 2-mercapto-6-nitrobenzothiazole, acrylic acid, DMF and 2, 2-dimethylolpropionic acid is 0.1mol:0.1mol:30-40mL:0.2-0.3g.

3. The method of claim 2, wherein the ultraviolet light is near ultraviolet light.

4. The method for preparing the high Wen Danyou lubricant according to claim 2, wherein the dosage ratio of carboxylated intermediate, pentaerythritol, toluene sulfonic acid, dioxane and water is 0.4mol:0.1mol:0.1-0.15g:50-100mL:80-150mL.

5. The method for preparing a high Wen Danyou lubricant according to claim 4, wherein the ratio of the amount of the branched esterified substance, sodium sulfide, sodium thiosulfate to the aqueous DMF is 100g:1.3-1.5g:0.5-0.8g:220mL.

6. The method for preparing a high Wen Danyou lubricant according to claim 5, wherein the amount ratio of the aminated ester, chlorosulfonic acid and absolute ethanol is 100g:0.4mol:260mL.

7. A high Wen Danyou lubricant prepared by the method of any one of claims 1-6.