Magnesium alkyl benzene sulfonate detergent and preparation method thereof

Abstract

The invention discloses a magnesium alkyl benzene sulfonate detergent which is prepared from the following raw material components in parts by mass: 60-120 parts of base oil; 60 to 120 parts of alkyl benzene sulfonic acid; 1-30 parts of a first accelerant; 40 to 80 parts of a magnesium source; 60 to 360 parts of an organic solvent; 5 to 40 parts of alcohol; 5 to 40 parts of water; 5 to 25 parts of a second accelerant; 0.1 to 5 parts of a chelating agent; and 40-70 parts of carbon dioxide. The invention further discloses a preparation method of the magnesium alkyl benzene sulfonate detergent, the compounding stability of the high-base-number magnesium sulfonate and other additives is improved, the product yield is effectively improved and reaches 90% or above, and meanwhile the preparation method is good in applicability to magnesium oxide of different quality grades.

Description

Technical Field

[0001] The invention belongs to the technical field of lubricating oil additives, relates to an alkylbenzene sulfonate magnesium detergent, and also relates to a preparation method of the alkylbenzene sulfonate magnesium detergent. Background Art

[0002] In the lubricant additive market, metal detergents can be divided into calcium salts and magnesium salts according to the different alkali metals. Compared with calcium salt products, magnesium salts have the characteristics of high alkalinity and low ash content. As environmental emission regulations become increasingly stringent, higher requirements are placed on the ash content of lubricants. At the same time, magnesium salts play an important role in solving the problem of low-speed pre-ignition (LSPI), and the status of magnesium salt metal detergents is constantly improving.

[0003] The preparation of high-base magnesium sulfonate requires special reaction conditions and special promoters. The common promoter system is a combination of a first promoter and a second promoter. The first promoter is generally a macromolecular carboxylic acid promoter, such as alkyl succinic anhydride, stearic acid, etc., and the second promoter is mainly a small molecule acid, such as formic acid, acetic acid, salicylic acid, etc. For example, the Chinese patent authorization publication numbers are CN104403722A, CN106675699A, CN1369543A, CN1369543A, etc.

[0004] The current lubricating oil additives are mainly compounded according to the synergistic law between different single agents to form a composite agent technology. The compounding stability has always been the key issue of the single agent. The problem with the high-base magnesium sulfonate in the above-mentioned preparation method patent is that when compounded with other additives, there will be stability problems such as turbidity or precipitation. Summary of the invention

[0005] The purpose of the present invention is to provide an alkylbenzene sulfonate magnesium detergent, which solves the problem of poor stability of the alkylbenzene sulfonate magnesium detergent in the prior art.

[0006] Another object of the present invention is to provide a method for preparing the above-mentioned magnesium alkylbenzene sulfonate detergent.

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

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

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

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

[0011] The first accelerator is one of cyclohexane 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 accelerator 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 invention is a method for preparing an alkylbenzene sulfonate magnesium detergent, which is specifically implemented according to the following steps:

[0018] Step 1. Weigh the following according to mass fractions: 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. Add the base oil, alkylbenzene sulfonic acid, first accelerator, magnesium source, organic solvent and second accelerator weighed in step 1 into a three-necked flask with a stirrer, stir evenly and heat to 40° C. to 60° C. for neutralization reaction, the reaction time is 30 min to 100 min, to obtain a mixture A;

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

[0021] Step 4. Adding mixture B to mixture A by dropwise addition, and introducing carbon dioxide to perform a high alkalinity reaction; the carbon dioxide aeration rate is 30 ml / min to 50 ml / min, to obtain mixture C;

[0022] Step 5. Heat the mixture C to 110° C. to 160° C., remove water and methanol from the mixture, and obtain a mixture D;

[0023] Step 6: After the mixture D is cooled to room temperature, gasoline is added for dilution, the mixture is centrifuged to remove slag, and the solvent removed by distillation at a higher temperature is the magnesium alkylbenzene sulfonate detergent of the present invention.

[0024] The beneficial effects of the present invention are:

[0025] The product prepared by the present invention has a base value greater than 400 mgKOH / g, a magnesium content greater than 9.0%, and a kinematic viscosity of no more than 150 mm at 100°C. 2 / s, with excellent stability and high temperature detergency. Due to the introduction of the chelating agent, and the combination of the first promoter cyclohexane acid, alkyl salicylic acid, etc. and the second promoter small molecule base, the structure of the micellar particles of high base magnesium sulfonate is significantly improved, thereby improving the compounding stability of high base magnesium sulfonate and other additives. The preparation method of the present invention effectively improves the yield of the product to more than 90%, and the preparation method of the present invention has good applicability to magnesium oxide of different quality grades. DETAILED DESCRIPTION

[0026] The present invention is described in detail below in conjunction with specific implementation modes.

[0027] The present invention discloses a magnesium alkylbenzene sulfonate detergent, which is composed of the following raw material components in parts by mass:

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

[0029] Preferably, the base oil is at least one of a Class I base oil, a Class II base oil, a Class III base oil or a synthetic oil in the American Petroleum Institute classification, preferably a Class I base oil.

[0030] Preferably, the molecular weight of the alkylbenzene sulfonic acid is 350-500, the length of the alkyl carbon chain is 10-30, and the phenyl group is toluene or benzene.

[0031] Preferably, the first accelerator is one of cycloalkane 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, it is methanol or ethanol, preferably methanol.

[0035] Preferably, the second accelerator 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, aminotriacetic acid or methylenetriaminepentaacetic acid.

[0038] The preparation method of the magnesium alkylbenzene sulfonate detergent of the present invention is specifically implemented according to the following steps:

[0039] Step 1. Weigh the following according to mass fractions: 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;

[0040] Step 2. Add the base oil, alkylbenzene sulfonic acid, first accelerator, magnesium source, organic solvent and second accelerator weighed in step 1 into a three-necked flask with a stirrer, stir evenly and heat to 40° C. to 60° C. for neutralization reaction, the reaction time is 30 min to 100 min, to obtain a mixture A;

[0041] Step 3. Mix the water, alcohol and chelating agent weighed in step 1 to obtain a mixture B;

[0042] Step 4. Adding mixture B to mixture A by dropwise addition, and introducing carbon dioxide to perform a high alkalinity reaction; the carbon dioxide aeration rate is 30 to 50 ml / min, to obtain mixture C;

[0043] Step 5. Heat the mixture C to 110° C. to 160° C., remove water and methanol from the mixture, and obtain a mixture D;

[0044] Step 6. After the mixture D is cooled to room temperature, a solvent is added to dilute it, centrifuge to remove the residue, and heat up to distill the removed solvent, which is the magnesium alkylbenzene sulfonate detergent of the present invention.

[0045] The solvent in step 6 is gasoline.

[0046] Example 1

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

[0048] Step 1. Weigh the following according to mass fractions: 60 parts of a type I base oil; 60 parts of alkylbenzene sulfonic acid; 1 part of cyclohexane acid; 40 parts of magnesium oxide; 60 parts of straight-run gasoline; 40 parts of methanol; 40 parts of water; 25 parts of ammonia water; 5 parts of ethylenediaminetetraacetic acid; 70 parts of carbon dioxide;

[0049] Step 2. Add the Class I base oil, alkylbenzene sulfonic acid, cyclohexane acid, magnesium oxide, straight-run gasoline and ammonia water weighed in step 1 into a three-necked flask with a stirrer, stir evenly and heat to 40° C. for neutralization reaction for 30 min to obtain a mixture A;

[0050] Step 3. Mix the water, methanol and ethylenediaminetetraacetic acid weighed in step 1 to obtain a mixture B;

[0051] Step 4. Adding mixture B to mixture A by dropwise addition, and introducing carbon dioxide to perform a high alkalinity reaction; the carbon dioxide aeration rate is 30 ml / min, to obtain mixture C;

[0052] Step 5. Heat the mixture C to 110° C. to remove water and methanol from the mixture to obtain a mixture D;

[0053] Step 6: After the mixture D is cooled to room temperature, gasoline is added for dilution, the mixture is centrifuged to remove slag, and the solvent removed by distillation at a higher temperature is the magnesium alkylbenzene sulfonate detergent of the present invention.

[0054] Example 2

[0055] The preparation method of magnesium alkylbenzene sulfonate detergent is specifically implemented according to the following steps:

[0056] Step 1. Weigh the following according to mass: Class II base oil, 120 parts; alkylbenzene 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; aminotriacetic acid, 0.1 parts; carbon dioxide, 40 parts;

[0057] Step 2. Add the Class II base oil, alkylbenzene sulfonic acid, alkyl salicylic acid, magnesium oxide, toluene and urea weighed in step 1 into a three-necked flask with a stirrer, stir evenly and heat to 60° C. for neutralization reaction for 100 min to obtain a mixture A;

[0058] Step 3. Mix the water, ethanol and aminotriacetic acid weighed in step 1 to obtain a mixture B;

[0059] Step 4. Adding mixture B to mixture A by dropwise addition, and introducing carbon dioxide to perform a high alkalinity reaction; the carbon dioxide aeration rate is 50 ml / min, to obtain mixture C;

[0060] Step 5. Heat the mixture C to 160° C. to remove water and methanol from the mixture to obtain a mixture D;

[0061] Step 6: After the mixture D is cooled to room temperature, gasoline is added for dilution, the mixture is centrifuged to remove slag, and the solvent removed by distillation at a higher temperature is the magnesium alkylbenzene sulfonate detergent of the present invention.

[0062] Example 3

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

[0064] Step 1. Weigh the following according to mass fractions: 90 parts of Class III base oil; 90 parts of alkylbenzene sulfonic acid; 15 parts of cyclohexane acid; 60 parts of magnesium oxide; 100 parts of toluene; 20 parts of methanol; 20 parts of water; 15 parts of ethylenediamine; 2 parts of dimethylenetriaminepentaacetic acid; 55 parts of carbon dioxide;

[0065] Step 2. Add the three types of base oil, alkylbenzene sulfonic acid, cyclohexane acid, magnesium oxide, toluene and ethylenediamine weighed in step 1 into a three-necked flask with a stirrer, stir evenly and heat to 50° C. for neutralization reaction. The reaction time is 70 min to obtain a mixture A;

[0066] Step 3. Mix the water, methanol and dimethylenetriaminepentaacetic acid weighed in step 1 to obtain a mixture B;

[0067] Step 4. Adding mixture B to mixture A by dropwise addition, and introducing carbon dioxide to perform a high alkalinity reaction; the carbon dioxide aeration rate is 40 ml / min, to obtain mixture C;

[0068] Step 5. Heat the mixture C to 140° C. to remove water and methanol from the mixture to obtain a mixture D;

[0069] Step 6: After the mixture D is cooled to room temperature, gasoline is added for dilution, the mixture is centrifuged to remove slag, and the solvent removed by distillation at a higher temperature is the magnesium alkylbenzene sulfonate detergent of the present invention.

[0070] Example 4

[0071] Alkylbenzene sulfonate magnesium detergent, weigh according to mass parts:

[0072] Synthetic oil, 80 parts; alkylbenzene sulfonic acid, 80 parts; cyclohexane acid, 10 parts; magnesium oxide, 70 parts; straight-run gasoline, 200 parts; methanol, 30 parts; water, 30 parts; ethylenediamine, 30 parts; methylenetriaminepentaacetic acid, 3 parts; carbon dioxide, 50 parts.

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

[0074] Example 5

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

[0076] Step 1. Weigh the following according to mass: 100 parts of a type I base oil; 80 parts of alkylbenzene sulfonic acid; 10 parts of cyclohexane acid; 52 parts of magnesium oxide; 300 parts of straight-run gasoline; 30 parts of methanol; 30 parts of water; 20 parts of ammonia water; 2 parts of ethylenediaminetetraacetic acid; and 52 parts of carbon dioxide.

[0077] Step 2. Add the Class I base oil, alkylbenzene sulfonic acid, cyclohexane acid, magnesium oxide, straight-run gasoline and ammonia water weighed in step 1 into a three-necked flask with a stirrer, stir evenly and heat to 50° C. for neutralization reaction for 30 min to obtain a mixture A;

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

[0079] Step 4. Adding mixture B to mixture A by dropwise addition, and introducing carbon dioxide to perform a high alkalinity reaction; the carbon dioxide aeration rate is 100 ml / min, to obtain mixture C;

[0080] Step 5. Heat the mixture C to 110° C. to remove water and methanol from the mixture to obtain a mixture D;

[0081] Step 6: After the mixture D is cooled to room temperature, gasoline is added for dilution, the mixture is centrifuged to remove slag, and the solvent removed by distillation at a higher temperature is the magnesium alkylbenzene sulfonate detergent of the present invention.

[0082] Example 6

[0083] Alkylbenzene sulfonate magnesium detergent, weigh according to mass parts:

[0084] Class I base oil, 100 parts; alkylbenzene sulfonic acid, 80 parts; cyclohexane acid, 10 parts; magnesium oxide, 52 parts; straight-run gasoline, 360 parts; methanol, 30 parts; water, 30 parts; ammonia water, 20 parts; aminotriacetic acid, 2 parts; carbon dioxide, 52 parts.

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

[0086] Example 7

[0087] Alkylbenzene sulfonate magnesium detergent, weigh according to mass parts:

[0088] Class I base oil, 100 parts; alkylbenzene 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. Weigh the following according to mass: 100 parts of a type I base oil; 80 parts of alkylbenzene sulfonic acid; 10 parts of polyisobutylene maleic anhydride; 52 parts of magnesium oxide; 150 parts of straight-run gasoline; 20 parts of salicylic acid; 20 parts of methanol; 20 parts of water; and 52 parts of carbon dioxide.

[0091] Step 2. Add the Class I base oil, alkylbenzene sulfonic acid, polyisobutylene maleic anhydride, magnesium oxide, straight-run gasoline, salicylic acid, methanol and water weighed in step 1 into a three-necked flask with a stirrer, stir evenly and heat to 50° C. for neutralization reaction for 30 min to obtain a mixture A;

[0092] Step 3. introducing carbon dioxide into the mixture A at a ventilation rate of 100 ml / min to perform a high alkalinity reaction to obtain a mixture B;

[0093] Step 4. heating the mixture B to 110° C. to remove water and methanol from the mixture to obtain a mixture C;

[0094] Step 6. After cooling the mixture C to room temperature, gasoline is added to dilute it, centrifuge to remove slag, and heat up to distill to remove the solvent, which is Comparative Example 1.

[0095] Comparative Example 2

[0096] Weigh according to mass:

[0097] Class I base oil, 100 parts; alkylbenzene 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 the same as that of Comparative Example 1.

[0099] Comparative Example 3

[0100] Weigh according to mass:

[0101] Class I base oil, 100 parts; alkylbenzene sulfonic acid, 80 parts; alkyl salicylic acid, 10 parts; magnesium oxide, 52 parts; straight-run gasoline, 150 parts; ammonia water, 20 parts; carbon dioxide, 52 parts.

[0102] The preparation method is the same as that of Comparative Example 1.

[0103] Product performance and compound stability test:

[0104] The compound stability test is an oil sample prepared by mixing high-base magnesium sulfonate with calcium salicylate detergent, polyisobutylene succinimide ashless dispersant, ZDDP and base oil. The oil sample is then stirred and stored at 100°C for one month to observe the amount of solid precipitation. The high-temperature detergency test uses the internal combustion engine oil coking test method to measure the amount of coke deposited on the aluminum plate. The smaller the coking amount, the better the high-temperature detergency.

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

[0106] Table 1 Physical and chemical properties and compound stability results

[0107]

[0108] As can be seen from the table, since chelating agents were added when preparing high-base magnesium sulfonate, Examples 1-3 performed well in the composite stability test and no precipitation occurred. At the same time, the products of the examples were superior to the comparative examples in terms of yield, high-temperature detergency, etc. In addition, the magnesium oxide used in the examples contained different active products and could successfully prepare high-base magnesium sulfonate, indicating that the preparation method of the present invention has good applicability to magnesium oxide of different quality grades.

Claims

1. A magnesium alkylbenzene sulfonate detergent, characterized in that: The invention is composed of the following raw material components in parts by mass: base oil, 60 to 120 parts; alkylbenzene sulfonic acid, 60 to 120 parts; first promoter, 1 to 30 parts; magnesium source, 40 to 80 parts; organic solvent, 60 to 360 parts; alcohol, 5 to 40 parts; water, 5 to 40 parts; second promoter, 5 to 25 parts; chelating agent, 0.1 to 5 parts; carbon dioxide, 40 to 70 parts.

2. The magnesium alkylbenzene sulfonate detergent according to claim 1, characterized in that The base oil is at least one of a Class I base oil, a Class II base oil, a Class III base oil or a synthetic oil in the American Petroleum Institute classification, preferably a Class I base oil.

3. The magnesium alkylbenzene sulfonate detergent according to claim 1, characterized in that: The molecular weight of the alkylbenzene sulfonic acid is 350-500, the length of the alkyl carbon chain is 10-30, and the phenyl group is toluene or benzene.

4. The magnesium alkylbenzene sulfonate detergent according to claim 1, characterized in that: The first promoter is one of cyclohexane acid or alkyl salicylic acid.

5. The magnesium alkylbenzene sulfonate detergent according to claim 1, characterized in that: The magnesium source is magnesium oxide.

6. The magnesium alkylbenzene sulfonate detergent according to claim 1, characterized in that: The organic solvent is one of straight-run gasoline or toluene.

7. The magnesium alkylbenzene sulfonate detergent according to claim 1, characterized in that: The alcohol is methanol or ethanol, preferably methanol.

8. The magnesium alkylbenzene sulfonate detergent according to claim 1, characterized in that: The second accelerator is one of ammonia water, urea or ethylenediamine.

9. The magnesium alkylbenzene sulfonate detergent according to claim 1, characterized in that: The chelating agent is an aminocarboxylic acid; the aminocarboxylic acid is one of ethylenediaminetetraacetic acid, aminotriacetic acid or dimethylenetriaminepentaacetic acid.

10. A method for preparing a magnesium alkylbenzene sulfonate detergent, characterized in that: Follow the steps below to implement it: Step 1. Weigh the following according to mass fractions: 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; Step 2. Add the base oil, alkylbenzene sulfonic acid, first accelerator, magnesium source, organic solvent and second accelerator weighed in step 1 into a three-necked flask with a stirrer, stir evenly and heat to 40° C. to 60° C. for neutralization reaction, the reaction time is 30 min to 100 min, to obtain a mixture A; Step 3. Mix the water, alcohol and chelating agent weighed in step 1 to obtain a mixture B; Step 4. Adding mixture B to mixture A by dropwise addition, and introducing carbon dioxide to perform a high alkalinity reaction; the carbon dioxide aeration rate is 30 ml / min to 50 ml / min, to obtain mixture C; Step 5. Heat the mixture C to 110° C. to 160° C., remove water and methanol from the mixture, and obtain a mixture D; Step 6: After the mixture D is cooled to room temperature, gasoline is added for dilution, the mixture is centrifuged to remove slag, and the solvent removed by distillation at a higher temperature is the magnesium alkylbenzene sulfonate detergent of the present invention.

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