CN115417832A

CN115417832A - High-temperature-resistant petroleum lubricant and preparation method thereof

Info

Publication number: CN115417832A
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: 2022-12-02
Anticipated expiration: 2042-10-12
Also published as: CN115417832B

Abstract

The invention relates to a high-temperature-resistant petroleum lubricant and a preparation method thereof, belonging to the technical field of petrochemical industry. The lubricant takes 2-mercapto-6-nitrobenzothiazole containing sulfur and nitrogen heterocycles as a functional raw material, carboxyl is grafted through acrylic acid addition, and then the esterified product is esterified with pentaerythritol to prepare an esterified product containing branched sulfur and nitrogen heterocycles, the esterified product and a drill rod substrate generate a multi-site anchoring effect, the adsorption strength of a lubricating film is enhanced, the lubricating film is not easy to fall off and lose efficacy under the working conditions of high load pressure and high friction heat, and the effect of heat-resistant lubrication is achieved; the nitro group is reduced into amino group, and strong hydrophilic sulfonic group is introduced into the end part through chlorosulfonic acid and the substitution modification thereof, so that the lubricant disclosed by the invention has good water solubility, can be used as an additive of water-based drilling fluid, and is more environment-friendly.

Description

High-temperature-resistant petroleum lubricant and preparation method thereof

Technical Field

The invention belongs to the technical field of petrochemical industry, and particularly relates to a high-temperature-resistant petroleum lubricant and a preparation method thereof.

Background

Frictional 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 lubricating agent, 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 selects mineral oil such as crude oil, engine oil, diesel oil and the like, the oil component contains a large amount of high-viscosity colloid, an oil film can be formed between a drilling tool and a rock wall, certain stability is kept, but the mineral oil is difficult to naturally decompose, has potential safety hazards, has large performance change along with temperature and is gradually replaced.

In the prior art, synthetic ester is used for replacing mineral oil, so that the negative effects that the conventional mineral oil and asphalt products are difficult to biodegrade and have serious pollution to the environment are changed, the waste treatment cost of the drilling fluid can be greatly reduced, and the adverse effect of the waste drilling fluid on the environment is relieved. However, a large amount of heat is generated in the drilling process, the rheological property difference of the existing synthetic ester is large in a high-heat environment, and a stable lubricating film is difficult to form between a drill rod and a rock wall; the present application is therefore directed to developing 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-temperature-resistant petroleum lubricant and a preparation method thereof.

The purpose of the invention can be realized by the following technical scheme:

the preparation method of the high-temperature-resistant petroleum lubricant specifically comprises the following steps:

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

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

The specific reaction process is as follows:

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

further, the amount ratio of the carboxylated intermediate, pentaerythritol, toluenesulfonic 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 a DMF (dimethyl formamide) aqueous solution under the protection of nitrogen, adding a branched ester, mixing, heating to 60 ℃, stirring and reducing for 3 hours, wherein nitro in the branched ester is reduced into amino, so as to prepare an aminated ester;

further, the dosage ratio of the branched ester, the sodium sulfide, the sodium thiosulfate and the DMF aqueous solution is 100g:1.3-1.5g:0.5-0.8g:220mL.

The specific reaction process is as follows:

step A4: mixing the aminated ester and anhydrous ethanol under the protection of nitrogen, heating to 40-50 ℃, setting the stirring speed at 600rpm, dropwise adding chlorosulfonic acid, stirring for reaction for 20min, adding water for mixing after the reaction is finished, and performing reduced pressure rotary evaporation to obtain a high-temperature resistant petroleum lubricant;

further, the dosage ratio of the aminated ester, chlorosulfonic acid and absolute ethyl alcohol is 100g:0.4mol:260mL.

The specific reaction process is as follows:

the invention has the beneficial effects that:

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

2. According to the invention, acrylic acid reacts with 2-mercapto-6-nitrobenzothiazole, carboxyl is grafted, and then esterification is carried out with pentaerythritol to prepare the ester containing the branched azothioheterocycle, on one hand, the ester has a certain lubricating effect and plays a role in auxiliary lubrication, on the other hand, the branched azothioheterocycle and a drill rod substrate generate a multi-site anchoring effect to enhance the adsorption strength of a lubricating film, and the lubricating film is not easy to fall off and lose efficacy under the working conditions of high pressure and high friction heat, so that the high temperature resistance is shown.

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

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

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

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

a2, adding dioxane and water into a reaction kettle, stirring and mixing the dioxane and the water 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, removing the solvent by rotary evaporation after the reaction is finished, and obtaining a branched esterified substance, wherein in the reaction, the dosage ratio of the carboxylated intermediate, the pentaerythritol, the toluenesulfonic acid, the dioxane and the water is 0.4mol:0.1mol:0.1g:50mL of: 150mL.

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

and a4, introducing nitrogen into the reaction kettle for protection, mixing the aminated ester and the absolute ethyl alcohol, heating to 40 ℃, controlling the stirring speed to be 600rpm, dropwise adding chlorosulfonic acid, controlling the dropwise adding speed to be 10mL/min, continuing stirring for 20min after dropwise adding, adding water with the volume of 1/5 of that of the reaction liquid after the reaction is finished, stirring and mixing, and then carrying out reduced pressure rotary evaporation to remove water and ethyl alcohol to obtain the high-temperature-resistant petroleum lubricant, wherein in the reaction, the dosage ratio of the aminated ester, 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 (dimethyl formamide) into a reaction kettle for mixing, preheating to 50 ℃, stirring for dissolving, then adding 2, 2-dimethylolpropionic acid, setting the stirring speed to 240rpm, heating to 100 ℃, applying near ultraviolet irradiation, wherein the irradiation distance is 20cm, the irradiation reaction time is 3h, adding methanol after the reaction is finished, reducing pressure, performing rotary evaporation and purification to obtain a carboxylated intermediate, wherein in the above reaction, the dosage ratio of the 2-mercapto-6-nitrobenzothiazole, the acrylic acid, the DMF and the 2, 2-dimethylolpropionic acid is 0.1mol:0.1mol:40mL of: 0.3g.

a2, adding dioxane and water into a reaction kettle, stirring and mixing the dioxane and the water to serve as a solvent, adding a carboxylated intermediate and pentaerythritol, stirring and dissolving the mixture, adding p-toluenesulfonic acid, heating to 106 ℃, refluxing for 2 hours, removing the solvent by rotary evaporation after the reaction is finished, and obtaining a branched esterified substance, wherein in the reaction, the dosage ratio of the carboxylated intermediate, the pentaerythritol, the toluenesulfonic acid, the dioxane and the water is 0.4mol:0.1mol:0.15g:100mL of: 80mL.

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

and a4, introducing nitrogen into the reaction kettle for protection, mixing the aminated ester and the absolute ethyl alcohol, heating to 50 ℃, controlling the stirring speed to be 600rpm, dropwise adding chlorosulfonic acid, controlling the dropwise adding speed to be 10mL/min, continuing stirring for 20min after dropwise adding, adding water with the volume of 1/5 of that of the reaction liquid after the reaction is finished, stirring and mixing, and then carrying out reduced pressure rotary evaporation to remove water and ethyl alcohol to obtain the high-temperature-resistant petroleum lubricant, wherein in the reaction, the dosage ratio of the aminated ester, the chlorosulfonic acid and the absolute ethyl alcohol is 100g:0.4mol:260mL.

Example 3

The high-temperature resistant petroleum lubricant is prepared by the following specific implementation process:

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

and a2, adding dioxane and water into a reaction kettle, stirring and mixing to serve as a solvent, adding a carboxylated intermediate and pentaerythritol, stirring and dissolving, adding p-toluenesulfonic acid, heating to 105 ℃, refluxing for 2.8 hours, and removing the solvent by rotary evaporation after the reaction is finished to obtain a branched esterified product, wherein in the reaction, the dosage ratio of the carboxylated intermediate, the pentaerythritol, the toluenesulfonic acid, the dioxane and the water is 0.4mol:0.1mol:0.13g:80mL of: 100mL.

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

and a4, introducing nitrogen into the reaction kettle for protection, mixing the aminated ester and the absolute ethyl alcohol, heating to 40-50 ℃, controlling the stirring speed to be 600rpm, dropwise adding chlorosulfonic acid, controlling the dropwise adding speed to be 10mL/min, continuing to stir for 20min after dropwise adding, adding water with the volume of 1/5 of the reaction liquid after the reaction is finished, stirring and mixing, and then carrying out reduced pressure rotary evaporation to remove water and ethyl alcohol to obtain the high-temperature-resistant petroleum lubricant, wherein in the reaction, the dosage ratio of the aminated ester, 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 (dimethyl formamide) into a reaction kettle for mixing, preheating to 50 ℃, stirring for dissolving, then adding 2, 2-dimethylolpropionic acid, setting the stirring speed to 240rpm, heating to 106 ℃, applying near ultraviolet irradiation, wherein the irradiation distance is 20cm, the irradiation reaction time is 3.6h, adding methanol after the reaction is finished, decompressing, carrying out rotary evaporation and purification to obtain a carboxylated intermediate, wherein in the above reaction, the dosage ratio of the 2-mercapto-6-nitrobenzothiazole, the acrylic acid, the DMF and the 2, 2-dimethylolpropionic acid is 0.1mol:0.1mol:35mL of: 0.28g.

a2, adding dioxane and water into a reaction kettle, stirring and mixing the dioxane and the water to serve as a solvent, adding a carboxylated intermediate and pentaerythritol, stirring and dissolving the mixture, adding p-toluenesulfonic acid, heating to 104 ℃, refluxing for 2.5 hours, removing the solvent by rotary evaporation after the reaction is finished, and obtaining a branched esterified product, wherein in the reaction, the dosage ratio of the carboxylated intermediate, the pentaerythritol, the toluenesulfonic acid, the dioxane and the water is 0.4mol:0.1mol:0.15g:90mL of: 110mL.

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

and a4, introducing nitrogen into the reaction kettle for protection, mixing the aminated ester and the absolute ethyl alcohol, heating to 40-50 ℃, controlling the stirring speed to be 600rpm, dropwise adding chlorosulfonic acid, controlling the dropwise adding speed to be 10mL/min, continuing to stir for 20min after dropwise adding, adding water with the volume of 1/5 of the volume of the reaction solution after the reaction is finished, stirring and mixing, and then carrying out reduced pressure rotary evaporation to remove water and ethanol to obtain the high-temperature-resistant petroleum lubricant, wherein in the reaction, the dosage ratio of the aminated ester, the chlorosulfonic acid and the absolute ethyl alcohol is 100g:0.4mol:260mL.

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

taking the following components in parts by weight:

22 portions of regenerated machine oil as base oil

10 parts of the high temperature resistant petroleum lubricant prepared in the above examples

3 parts of sodium dodecyl benzene sulfonate as a surfactant

5 parts of emulsifier OP-10 as emulsifier

2 parts of sodium carboxymethylcellulose as a 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 and stirred and mixed at a high speed of 1800rpm for 10min to prepare the emulsion-shaped drilling fluid.

Comparative example 1

The drilling fluid is prepared by the comparative example, and the high-temperature-resistant petroleum lubricant is replaced by the base oil with the same weight part.

The drilling fluid compounded by the components is tested according 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 invention meets the use standard of the lubricant for the drilling fluid, wherein the reduction rate of the lubrication coefficient reaches 91.47-93.65%, and the lubricant shows excellent lubrication performance.

The drilling fluid compounded by the components is subjected to temperature resistance tests at 100 ℃, 120 ℃, 140 ℃ and 160 ℃, and the 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 small change rate of rheological property and friction coefficient along with temperature rise and keeps stable lubricating effect.

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

TABLE 3

As can be seen from the data in Table 3, the lubricating film strength 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 ℃, so that the stable lubricating effect is maintained.

In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to 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 invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. 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 illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.

Claims

1. The preparation method of the high-temperature-resistant petroleum lubricant is characterized by comprising 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 ℃, stirring under ultraviolet irradiation for reaction for 3-4h to obtain a carboxylated intermediate;

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

step A3: dissolving sodium sulfide and sodium thiosulfate in a DMF (dimethyl formamide) aqueous 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 aminated ester and absolute ethyl alcohol under the protection of nitrogen, heating to 40-50 ℃, setting the stirring speed at 600rpm, dropwise adding chlorosulfonic acid, stirring for reaction for 20min, adding water for mixing after the reaction is finished, and carrying out reduced pressure rotary evaporation to obtain the high-temperature-resistant petroleum lubricant.

2. The method of claim 1, wherein the 2-mercapto-6-nitrobenzothiazole, acrylic acid, DMF, and 2, 2-dimethylolpropionic acid are used in a ratio of 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 a high temperature resistant petroleum lubricant as claimed in claim 2, wherein the amount ratio of the carboxylated intermediate, pentaerythritol, methyl benzene sulfonic acid, dioxane and water is 0.4mol:0.1mol:0.1-0.15g:50-100mL:80-150mL.

5. The method for preparing the high-temperature-resistant petroleum lubricant according to claim 4, wherein the ratio of the amount of the branched ester to the amount of the sodium sulfide to the amount of the sodium thiosulfate to the amount of the DMF aqueous solution is 100g:1.3-1.5g:0.5-0.8g:220mL.

6. The method for preparing a high temperature resistant petroleum lubricant as claimed in claim 5, wherein the amount ratio of the aminated ester, chlorosulfonic acid and absolute ethyl alcohol is 100g:0.4mol:260mL.

7. A high temperature resistant petroleum lubricant, characterized by being produced by the method of any one of claims 1 to 6.