Magnesium alkylbenzenesulfonate detergents and process for their preparation

Abstract

The application discloses a kind of alkyl benzene sulfonic acid magnesium detergent, by following raw material components according to mass fraction is formed: base oil, 60~120 parts;Alkyl benzene sulfonic acid, 60~120 parts;First accelerator, 1~30 parts;Magnesium source, 40~80 parts;Organic solvent, 60~360 parts;Alcohol, 5~40 parts;Water, 5~40 parts;Second accelerator, 5~25 parts;Chelating agent, 0.1~5 parts;Carbon dioxide, 40~70 parts.The application also discloses the preparation method of alkyl benzene sulfonic acid magnesium detergent, the application improves the compounding stability of high base value sulfonic acid magnesium and other additives, effectively improves the yield of product, reaches 90% or more, meanwhile, the preparation method of the application is good in applicability to different quality grades of magnesium oxide.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of lubricating oil additives, and relates to a magnesium alkylbenzenesulfonate detergent. BACKGROUND

[0002] In the lubricating oil additive market, according to the difference of alkali metal of metal detergent, it can be divided into calcium salt and magnesium salt, etc. Among them, the magnesium salt has the characteristics of high base value and low ash content compared with the calcium salt product. With the increasingly stringent environmental emission regulations, higher requirements are put forward for the ash content of lubricating oil, and the magnesium salt plays an important role in solving the problem of low speed pre-ignition (LSPI), so the position of the magnesium salt metal detergent is continuously improved.

[0003] The preparation of high base value magnesium sulfonate needs special reaction conditions and special accelerators. The common accelerator system is the combination of a first accelerator and a second accelerator. The first accelerator is generally a macromolecular carboxylic acid accelerator, such as hydrocarbyl succinic anhydride, stearic acid, etc., and the second accelerator is mainly a small molecule acid, such as formic acid, acetic acid, salicylic acid, etc. For example, Chinese patents with authorized publication numbers CN104403722A, CN106675699A, CN1369543A, CN1369543A, etc.

[0004] At present, the lubricating oil additive is mainly a complex agent technology formed by compounding according to the nature synergy law between different single agents, and the stability of compounding has been a key problem of the single agent. The high base value magnesium sulfonate in the above preparation method patent has the problem that turbidity or precipitation and other stability problems may occur when it is compounded with other additives. SUMMARY

[0005] The purpose of the present application is to provide a magnesium alkylbenzenesulfonate detergent, which solves the problem of poor stability of the magnesium alkylbenzenesulfonate detergent in the prior art.

[0006] Another purpose of the present application is to provide a preparation method of the magnesium alkylbenzenesulfonate detergent.

[0007] The technical scheme adopted by the present application is that the magnesium alkylbenzenesulfonate detergent is composed of the following raw material components in mass fraction: base oil, 60-120 parts; alkylbenzenesulfonic acid, 60-120 parts; first accelerator, 1-30 parts; magnesium source, 40-80 parts; organic solvent, 60-360 parts; alcohol, 5-40 parts; water, 5-40 parts; second accelerator, 5-25 parts; chelating agent, 0.1-5 parts; and carbon dioxide, 40-70 parts.

[0008] The present application is also characterized in that:

[0009] The base oil is at least one of Group I base oil, Group II base oil, Group III base oil or synthetic oil in the American Petroleum Institute classification, preferably Group I base oil.

[0010] The alkylbenzene sulfonic acid has a molecular weight of 350-500, an alkyl carbon chain length of 10-30, and a benzene group of toluene or benzene.

[0011] The first promoter is one of naphthenic acid or alkyl salicylic acid.

[0012] The magnesium source is magnesium oxide.

[0013] The organic solvent is one of straight-run gasoline or toluene.

[0014] The alcohol is methanol or ethanol, preferably methanol.

[0015] The second promoter is one of ammonia, urea or ethylenediamine.

[0016] The chelating agent is an aminocarboxylic acid; the aminocarboxylic acid is one of ethylenediaminetetraacetic acid, aminotriacetic acid or dimethylenetriaminepentaacetic acid.

[0017] Another technical solution adopted by the present application is a preparation method of magnesium alkylbenzene sulfonate detergent, which is specifically implemented according to the following steps:

[0018] Step 1. According to the mass fraction, the following components are weighed: base oil, 60-120 parts; alkylbenzene sulfonic acid, 60-120 parts; first promoter, 1-30 parts; magnesium source, 40-80 parts; organic solvent, 10-250 parts; alcohol, 5-40 parts; water, 5-40 parts; second promoter, 5-25 parts; chelating agent, 0.1-5 parts; carbon dioxide, 40-70 parts;

[0019] Step 2. The base oil, alkylbenzene sulfonic acid, first promoter, magnesium source, organic solvent and second promoter weighed in step 1 are added to a three-necked flask with a stirrer, stirred uniformly and heated to 40-60°C for neutralization reaction, the reaction time is 30-100 minutes, and a mixture A is obtained;

[0020] Step 3. The water, alcohol and chelating agent weighed in step 1 are mixed to obtain a mixture B;

[0021] Step 4. The mixture B is added to the mixture A by dropwise addition, and carbon dioxide is introduced for high alkalinity reaction; the gasification rate of the carbon dioxide is 30-50 ml / min, and a mixture C is obtained;

[0022] Step 5. The mixture C is heated to 110-160°C to remove water and methanol in the mixture, and a mixture D is obtained;

[0023] Step 6. After the mixture D is cooled to room temperature, gasoline is added to dilute the mixture, and the residue is removed by centrifugation. The solvent is distilled off at elevated temperature to obtain the magnesium alkylbenzenesulfonate detergent of the present application.

[0024] The present application has the following advantages:

[0025] The product prepared by the present application has a base number greater than 400 mgKOH / g, a magnesium content greater than 9.0%, and a kinematic viscosity at 100℃ not greater than 150 mm 2 / s, and excellent stability and high-temperature detergency. The structure of the micellar particles of the high-base-number magnesium sulfonate is significantly improved due to the introduction of the chelating agent and the combination of the first promoter (naphthenic acid, alkyl salicylic acid, etc.) and the second promoter (small-molecule base), thereby improving the compounding stability of the high-base-number magnesium sulfonate with other additives. The preparation method of the present application effectively improves the yield of the product to more than 90%, and is suitable for different quality grades of magnesium oxide. DETAILED DESCRIPTION

[0026] The present application will be described in detail below with reference to specific embodiments.

[0027] The magnesium alkylbenzenesulfonate detergent of the present application is composed of the following raw material components in mass fractions:

[0028] Base oil, 100 parts; alkylbenzenesulfonic acid, 60-120 parts; first promoter, 1-30 parts; magnesium source, 40-80 parts; organic solvent, 10-250 parts; alcohol, 5-40 parts; water, 5-40 parts; second promoter, 5-25 parts; chelating agent, 0.1-5 parts; carbon dioxide, 40-70 parts.

[0029] Preferably, the base oil is at least one of Group I base oil, Group II base oil, Group III base oil, or synthetic oil according to the American Petroleum Institute classification, and is preferably Group I base oil.

[0030] Preferably, the alkylbenzenesulfonic acid has a molecular weight of 350-500, an alkyl carbon chain length of 10-30, and a phenyl group of toluene or benzene.

[0031] Preferably, the first promoter is one of naphthenic acid or alkyl salicylic acid.

[0032] Preferably, the magnesium source is magnesium oxide.

[0033] Preferably, the organic solvent is one of straight-run gasoline or toluene.

[0034] Preferably, the alcohol is methanol or ethanol, and is preferably methanol.

[0035] Preferably, the second promoter is one of ammonia, urea, or ethylenediamine.

[0036] Preferably, the chelating agent is an aminocarboxylic acid.

[0037] Preferably, the aminocarboxylic acid is one of ethylenediaminetetraacetic acid, amino triacetic acid or dimethylenetriamine pentaacetic acid.

[0038] The preparation method of the magnesium alkylbenzenesulfonate detergent of the present application is implemented according to the following steps:

[0039] Step 1. According to the mass fraction, the following are weighed: base oil, 60-120 parts; alkylbenzenesulfonic acid, 60-120 parts; first promoter, 1-30 parts; magnesium source, 40-80 parts; organic solvent, 10-250 parts; alcohol, 5-40 parts; water, 5-40 parts; second promoter, 5-25 parts; chelating agent, 0.1-5 parts; carbon dioxide, 40-70 parts;

[0040] Step 2. The base oil, alkylbenzenesulfonic acid, first promoter, magnesium source, organic solvent and second promoter weighed in Step 1 are added to a three-necked flask with a stirrer, stirred uniformly and heated to 40-60°C for neutralization reaction, the reaction time being 30-100 minutes, to obtain a mixture A;

[0041] Step 3. The water, alcohol and chelating agent weighed in Step 1 are mixed to obtain a mixture B;

[0042] Step 4. The mixture B is added to the mixture A by dropwise addition, and carbon dioxide is introduced for high-alkalinity reaction; the carbon dioxide is introduced at a rate of 30-50 ml / min to obtain a mixture C;

[0043] Step 5. The mixture C is heated to 110-160°C to remove water and methanol in the mixture, to obtain a mixture D;

[0044] Step 6. After the mixture D is cooled to room temperature, a solvent is added for dilution, centrifugation is performed to remove slag, and the solvent distilled off at elevated temperature is the magnesium alkylbenzenesulfonate detergent of the present application.

[0045] The solvent in Step 6 is gasoline.

[0046] Example 1

[0047] The preparation method of the magnesium alkylbenzenesulfonate detergent is implemented according to the following steps:

[0048] Step 1. According to the mass fraction, the following are weighed: one type of base oil, 60 parts; alkylbenzenesulfonic acid, 60 parts; naphthenic acid, 1 part; magnesium oxide, 40 parts; straight-run gasoline, 60 parts; methanol, 40 parts; water, 40 parts; ammonia water, 25 parts; ethylenediaminetetraacetic acid, 5 parts; carbon dioxide, 70 parts;

[0049] Step 2. The first step of weighing a kind of base oil, alkyl benzene sulfonic acid, naphthenic acid, magnesium oxide, straight-run gasoline, ammonia water into a three-necked flask with a stirrer, stirring evenly and heating to 40℃ for neutralization reaction, the reaction time is 30min, to obtain mixture A;

[0050] Step 3. The water, methanol and ethylenediaminetetraacetic acid weighed in step 1 are mixed to obtain mixture B;

[0051] Step 4. Mixture B is added to mixture A by dropwise addition, and carbon dioxide is introduced to carry out high alkalinity reaction; the gasification rate of the carbon dioxide is 30ml / min, to obtain mixture C;

[0052] Step 5. Mixture C is heated to 110℃, and the water and methanol in the mixture are removed to obtain mixture D;

[0053] Step 6. After mixture D is cooled to room temperature, gasoline is added for dilution, centrifugal slag removal, and the solvent distilled at elevated temperature is the alkyl benzene sulfonic acid magnesium detergent of the application.

[0054] Example 2

[0055] The preparation method of the alkyl benzene sulfonic acid magnesium detergent is specifically implemented according to the following steps:

[0056] Step 1. According to the mass fraction, the following are weighed: second type base oil, 120 parts; alkyl benzene sulfonic acid, 120 parts; alkyl salicylic acid, 30 parts; magnesium oxide, 80 parts; toluene, 360 parts; ethanol, 5 parts; water, 5 parts; urea, 5 parts; amino triacetic acid, 0.1 parts; carbon dioxide, 40 parts;

[0057] Step 2. The second type base oil, alkyl benzene sulfonic acid, alkyl salicylic acid, magnesium oxide, toluene and urea weighed in step 1 are added to a three-necked flask with a stirrer, stirred evenly and heated to 60℃ for neutralization reaction, the reaction time is 100min, to obtain mixture A;

[0058] Step 3. The water, ethanol and amino triacetic acid weighed in step 1 are mixed to obtain mixture B;

[0059] Step 4. Mixture B is added to mixture A by dropwise addition, and carbon dioxide is introduced to carry out high alkalinity reaction; the gasification rate of the carbon dioxide is 50ml / min, to obtain mixture C;

[0060] Step 5. Mixture C is heated to 160℃, and the water and methanol in the mixture are removed to obtain mixture D;

[0061] Step 6. After mixture D is cooled to room temperature, gasoline is added for dilution, centrifugal slag removal, and the solvent distilled at elevated temperature is the alkyl benzene sulfonic acid magnesium detergent of the application.

[0062] Example 3

[0063] The preparation method of the magnesium alkylbenzenesulfonate detergent is specifically implemented according to the following steps:

[0064] Step 1. According to mass fraction, the following components are weighed: three types of base oil, 90 parts; alkylbenzenesulfonic acid, 90 parts; naphthenic acid, 15 parts; magnesium oxide, 60 parts; toluene, 100 parts; methanol, 20 parts; water, 20 parts; ethylenediamine, 15 parts; dimethylenetriamine pentaacetate, 2 parts; carbon dioxide, 55 parts;

[0065] Step 2. The three types of base oil, alkylbenzenesulfonic acid, naphthenic acid, magnesium oxide, toluene and ethylenediamine weighed in step 1 are added to a three-necked flask with a stirrer, stirred uniformly and heated to 50℃ for neutralization reaction, the reaction time is 70 min, and mixture A is obtained;

[0066] Step 3. The water, methanol and dimethylenetriamine pentaacetate weighed in step 1 are mixed to obtain mixture B;

[0067] Step 4. Mixture B is added to mixture A by dropwise addition, and carbon dioxide is introduced for high alkalinity reaction; the aeration rate of the carbon dioxide is 40 ml / min, and mixture C is obtained;

[0068] Step 5. Mixture C is heated to 140℃ to remove water and methanol in the mixture, and mixture D is obtained;

[0069] Step 6. After mixture D is cooled to room temperature, gasoline is added for dilution, centrifugation is performed to remove slag, and the solvent distilled at elevated temperature is the magnesium alkylbenzenesulfonate detergent of the application.

[0070] Example 4

[0071] The magnesium alkylbenzenesulfonate detergent is weighed according to mass fraction:

[0072] Synthetic oil, 80 parts; alkylbenzenesulfonic acid, 80 parts; naphthenic acid, 10 parts; magnesium oxide, 70 parts; straight-run gasoline, 200 parts; methanol, 30 parts; water, 30 parts; ethylenediamine, 30 parts; dimethylenetriamine pentaacetate, 3 parts; carbon dioxide, 50 parts.

[0073] The preparation method is as shown in Example 3.

[0074] Example 5

[0075] The preparation method of the magnesium alkylbenzenesulfonate detergent is specifically implemented according to the following steps:

[0076] Step 1. Take the following ingredients according to mass fraction: a kind of base oil, 100 parts; alkyl benzene sulfonic acid, 80 parts; naphthenic acid, 10 parts; magnesium oxide, 52 parts; straight-run gasoline, 300 parts; methanol, 30 parts; water, 30 parts; ammonia water, 20 parts; ethylenediaminetetraacetic acid, 2 parts; carbon dioxide, 52 parts;

[0077] Step 2. Put the a kind of base oil, alkyl benzene sulfonic acid, naphthenic acid, magnesium oxide, straight-run gasoline and ammonia water taken in Step 1 into a three-necked flask with a stirrer, stir uniformly and heat to 50℃ for neutralization reaction, the reaction time is 30 min, to obtain mixture A;

[0078] Step 3. Mix the water, methanol and ethylenediaminetetraacetic acid taken in Step 1 to obtain mixture B;

[0079] Step 4. Add mixture B to mixture A by dropwise method, and introduce carbon dioxide to carry out high alkalinity reaction; the gasification rate of carbon dioxide is 100 ml / min, to obtain mixture C;

[0080] Step 5. Heat mixture C to 110℃ to remove water and methanol in the mixture, to obtain mixture D;

[0081] Step 6. After mixture D is cooled to room temperature, add gasoline for dilution, centrifugal slag removal, and the solvent distilled out at elevated temperature is the alkyl benzene sulfonic acid magnesium detergent of the application.

[0082] Example 6

[0083] The alkyl benzene sulfonic acid magnesium detergent is taken according to mass fraction:

[0084] a kind of base oil, 100 parts; alkyl benzene sulfonic acid, 80 parts; naphthenic acid, 10 parts; magnesium oxide, 52 parts; straight-run gasoline, 360 parts; methanol, 30 parts; water, 30 parts; ammonia water, 20 parts; amino triacetic acid, 2 parts; carbon dioxide, 52 parts.

[0085] The preparation method is as shown in Example 5.

[0086] Example 7

[0087] The alkyl benzene sulfonic acid magnesium detergent is taken according to mass fraction:

[0088] a kind of base oil, 100 parts; alkyl benzene sulfonic acid, 80 parts; alkyl salicylic acid, 10 parts; magnesium oxide, 52 parts; straight-run gasoline, 300 parts; methanol, 30 parts; water, 30 parts; ammonia water, 20 parts; ethylenediaminetetraacetic acid, 2 parts; carbon dioxide, 52 parts;

[0089] Comparative Example 1

[0090] Step 1. Take by mass fraction: a kind of base oil, 100 parts; alkyl benzene sulfonic acid, 80 parts; polyisobutylene maleic anhydride, 10 parts; magnesium oxide, 52 parts; straight-run gasoline, 150 parts; salicylic acid, 20 parts; methanol, 20 parts; water, 20 parts; carbon dioxide, 52 parts;

[0091] Step 2. Add the a kind of base oil, alkyl benzene sulfonic acid, polyisobutylene maleic anhydride, magnesium oxide, straight-run gasoline, salicylic acid, methanol and water taken in step 1 into a three-necked flask with a stirrer, stir uniformly and heat to 50℃ for neutralization reaction, the reaction time is 30 min, to obtain mixture A;

[0092] Step 3. Introduce carbon dioxide into mixture A, the gas flow rate is 100 ml / min, to carry out high alkalinity reaction, to obtain mixture B;

[0093] Step 4. Heat mixture B to 110℃, to remove water and methanol in the mixture, to obtain mixture C;

[0094] Step 6. After mixture C is cooled to room temperature, add gasoline for dilution, centrifugal slag removal, and the solvent distilled out at elevated temperature is the product of Example 1.

[0095] Comparative Example 2

[0096] Take by mass fraction:

[0097] a kind of base oil, 100 parts; alkyl benzene sulfonic acid, 80 parts; stearic acid, 10 parts; magnesium oxide, 52 parts; straight-run gasoline, 150 parts; acetic acid, 20 parts; methanol, 30 parts; water, 30 parts; carbon dioxide, 52 parts.

[0098] The preparation method is as in Comparative Example 1.

[0099] Comparative Example 3

[0100] Take by mass fraction:

[0101] a kind of base oil, 100 parts; alkyl benzene sulfonic acid, 80 parts; alkyl salicylic acid, 10 parts; magnesium oxide, 52 parts; straight-run gasoline, 150 parts; ammonia, 20 parts; carbon dioxide, 52 parts.

[0102] The preparation method is as in Comparative Example 1.

[0103] Product performance and complex stability test:

[0104] The complex stability test is an oil sample prepared by mixing high-alkaline magnesium sulfonate, calcium salicylate detergent, polyisobutylene succinimide ashless dispersant, ZDDP and base oil, then the oil sample is stirred and stored at 100°C for one month, and the amount of solid precipitated is observed. The high-temperature detergency test is a test method for measuring the amount of coke deposited on an aluminum plate, and the smaller the amount of coke, the better the high-temperature detergency.

[0105] The product performance and complex stability test results are shown in Table 1:

[0106] Table 1: Physicochemical properties and complex stability results

[0107]

[0108] As can be seen from the table, examples 1-3, due to the addition of chelating agent in the preparation of high-alkaline magnesium sulfonate, perform excellently in the complex stability test, and no precipitation occurs. At the same time, the products of the examples are superior to the comparative examples in terms of yield, high-temperature detergency, etc. In addition, the magnesium oxide used in the examples contains different active products, and high-alkaline magnesium sulfonate can be successfully prepared, which indicates that the preparation method of the present application is suitable for different quality grades of magnesium oxide.

Claims

1. A magnesium alkylbenzenesulfonate detergent, characterized in that, The additive is composed of the following components by mass fraction: base oil, 60-120 parts; alkyl benzene sulfonic acid, 60-120 parts; first promoter, 1-30 parts; magnesium source, 40-80 parts; organic solvent, 60-360 parts; alcohol, 5-40 parts; water, 5-40 parts; second promoter, 5-25 parts; chelating agent, 0.1-5 parts; carbon dioxide, 40-70 parts; The first promoter is one of naphthenic acid or alkyl salicylic acid; The second promoter is one of ammonia, urea or ethylenediamine; The chelating agent is aminocarboxylic acid, which is one of ethylenediaminetetraacetic acid, amino triacetic acid or dimethylenetriamine pentaacetic acid.

2. The magnesium alkylbenzenesulfonate detergent of claim 1, wherein, The base oil is at least one of Group I base oil, Group II base oil, Group III base oil or synthetic oil in the American Petroleum Institute classification.

3. The magnesium alkylbenzenesulfonate detergent of claim 1, wherein, The alkyl benzene sulfonic acid has a molecular weight of 350-500, an alkyl carbon chain length of 10-30 and a phenyl group of toluene or benzene.

4. The magnesium alkylbenzenesulfonate detergent of claim 1, wherein, The magnesium source is magnesium oxide.

5. The magnesium alkylbenzenesulfonate detergent of claim 1, wherein, The organic solvent is one of straight-run gasoline or toluene.

6. The magnesium alkylbenzenesulfonate detergent of claim 1, wherein, The alcohol is methanol or ethanol.

7. The method of producing the magnesium alkylbenzenesulfonate detergent according to any one of claims 1 to 6, characterized by, The additive is prepared according to the following steps: Step 1. Take the following components by mass fraction: base oil, 60-120 parts; alkyl benzene sulfonic acid, 60-120 parts; first promoter, 1-30 parts; magnesium source, 40-80 parts; organic solvent, 60-360 parts; alcohol, 5-40 parts; water, 5-40 parts; second promoter, 5-25 parts; chelating agent, 0.1-5 parts; carbon dioxide, 40-70 parts; Step 2. Put the base oil, alkyl benzene sulfonic acid, first promoter, magnesium source, organic solvent and second promoter taken in Step 1 into a three-necked flask with a stirrer, stir uniformly and heat to 40-60°C for neutralization reaction, the reaction time is 30-100 min, to obtain mixture A; Step 3. Mix the water, alcohol and chelating agent taken in Step 1 to obtain mixture B; Step 4. Add mixture B to mixture A by dropwise addition and introduce carbon dioxide for high alkalinity reaction; the gas flow rate of carbon dioxide is 30-50 ml / min, to obtain mixture C; Step 5. Heat mixture C to 110-160°C to remove water and methanol in the mixture, to obtain mixture D; Step 6. After mixture D is cooled to room temperature, add gasoline for dilution, centrifuge to remove slag, heat and distill to remove the solvent, to obtain the alkyl benzene sulfonic acid magnesium detergent.

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