CN101638603B

CN101638603B - Method for improving quality of sulfonate detergent

Info

Publication number: CN101638603B
Application number: CN200810117475A
Authority: CN
Inventors: 曲江; 赵世权; 乔悦; 张玉东
Original assignee: China Petroleum and Natural Gas Co Ltd
Current assignee: China Petroleum and Natural Gas Co Ltd
Priority date: 2008-07-31
Filing date: 2008-07-31
Publication date: 2012-10-17
Anticipated expiration: 2028-07-31
Also published as: CN101638603A

Abstract

The invention relates to a method for improving the quality of a sulfonate detergent, which comprises the following steps: dissolving a sulfonate metal detergent into a solvent, adding 1 to 5 percent by weight of C1-5 low-grade fatty alkanol and 0.1 to 0.6 percent by weight of carboxylic acid in terms of 100 percent by weight of the sulfonate metal detergent, mixing the mixture evenly, then reacting the mixture for 1 to 3 hours at the temperature of between 60 and 90 DEG C, and obtaining the low-turbidity sulfonate metal detergent of which the turbidity is 150 to 200 JTU through distilling post treatment, wherein the solvent is fatty hydrocarbon or aromatic hydrocarbon of which the boiling point is less than 150 DEG C under atmospheric pressure. The method for improving the quality of the sulfonate detergent basically does not increase the cost, and has the advantages of simple process, convenience for adjusting and controlling, remarkable effect, strong applicability and excellent deterging property.

Description

A kind of method of improving quality of sulfonate detergent

Technical field

The present invention relates to a kind of method of improving high base number or overbased divalent alkaline-earth metal quality of sulfonate detergent.

Background technology

Sulfonate additive has excellent acid neutralization capacity and high temperature detergent performance, and rust-preventing characteristic is good, and certain dispersiveness is arranged, and is the comprehensive and most widely used lubricant oil metal detergent of a kind of performance.

The active principle of sulfonate additive generally is to be made up of at alkali or the lip-deep sulfonic acid normal salt of subsalt (carbonate or borate) alkali or subsalt (carbonate or borate) and absorption or complexing, is evenly distributed and particle diameter can the colloid discrete form stably be scattered in the oil solution less than the active principle of 80nm.So the ideal sulfonate detergent is the colloid oiliness thing of a kind of appearance transparent, stable performance.At present, the calcium sulfonate with high base number of carbonate type and overbased sulfonic acid magnesium are the kinds of generally using.

Owing to reasons such as raw material, synthesis mechanism and ME; Often contain in the sulfonate product that some are imperceptible, dispersive is non-or little oil-soluble substance; These are non-or the oily thing of slightly soluble is bigger to the use properties harm of lubricating oil; Though it is carried out qualitative accurately, quantitative analysis detection difficult, can characterize through turbidity (JTU) index of reflection optical property.The petroleum chemical industry standard SH/T 0028-90 of the People's Republic of China " detergent for lubricating oil tuurbidimetry " has promptly stipulated the measuring method of detergent for lubricating oil turbidity; The turbidity of measuring sulfonate detergent with this method generally should be less than 250JTU, and is better less than 200JTU.But the turbidity of the turbidity of sulfonate detergent, especially high base number or overbased divalent alkaline-earth metal sulfonate detergent product usually is higher than 250JTU, sometimes even be higher than more than the 400JTU.

Though it is a lot of that relevant sulfonate detergent production prepares patent; As: US6268318, US5578235, US 5108630, US 4997584, US 4929373, US 4880550, US 4879053, US 2616925 or the like; At present, have only CN03104813.7 to disclose a kind of turbidity for preparing less than 200JTU and contain the method for the high base number calcium mahogany sulfonate of 1.0～2.0% sodium Metal 99.5s.CN03104813.7 proposes: with mahogany acid and quicklime etc. is raw material; Introduce tensio-active agent and proper amount of sodium hydroxide such as alkyl salicylate, sulfenyl phenolate; Under the condition of promotor, with a certain proportion of ratio of components synthesized base number greater than 280mgKOH/g, Na% be 1.0～2.0, surfactant content greater than 5%, turbidity is less than the high base number calcium mahogany sulfonate of 200JTU.

Summary of the invention

The improvement method that the purpose of this invention is to provide a kind of method of improving quality of sulfonate detergent, especially high base number or overbased divalent alkaline-earth metal quality of sulfonate detergent.

The method of improving quality of sulfonate detergent that the present invention proposes is following: the sulphonate metal detergent is dissolved in the solvent; Organic alcohol of adding 0.5～15% and 0.05～15% acid; After mixing, reacted 1～5 hour down at 50～120 ℃, through post-processing steps such as distillations; Can make turbidity less than 200JTU, even less than the low turbidity sulphonate metal detergent of 150JTU.

The sulphonate metal detergent is to be the main raw material preparation by mahogany acid or synthetic sulfonic acid and metal hydroxides or oxide compound; Get final product carbonate containing in the sulphonate, but also boracic hydrochlorate; Metals ion can be divalent alkaline-earth metals such as calcium, magnesium, barium in the sulphonate, also can be monovalent base metals ions such as sodium, potassium.What particularly point out is that the sulphonate metal detergent can be the finished product of production equipment, also can be the thick product or the work in-process of any process step of carbonating or boration end back in the production line.The present invention is especially suitable for the turbidity and the cleansing performance of high base number that improves carbonate type or overbased divalent alkaline-earth metal sulfonate detergent.

Solvent is all or part of therein soluble hydrocarbon solvent of a kind of sulphonate, and preferred atmosphere is depressed the hydrocarbon solvent that boiling point is lower than 150 ℃.Suitable hydrocarbon solvent has aliphatic hydrocarbon and aromatic hydrocarbon, like hexane, heptane, benzene,toluene,xylene, propyl carbinol, sherwood oil etc.Solvent load is so that the system material viscosity is moderate is as the criterion, and those skilled in the art can rule of thumb judge with general knowledge.

Organic alcohol is generally the mixture of C1～5 lower aliphatic alkanols and two or more this type alcohol, suitable alkanol such as methyl alcohol, ethanol, Virahol, butanols, amylalcohol etc., particular methanol.The consumption of lower aliphatic alkanol is generally 0.5～15%, and preferred 1～5%.

Acid among the present invention can be organic acid or mineral acid, suitable acid such as sulfonic acid, alkene acid anhydride, alkenyl succinic acid, Whitfield's ointment, naphthenic acid, alkylbenzoic acid, formic acid, acetate, boric acid etc., and the low carbon chain carboxylic acid is better, preferable formic acid.The consumption of acid is generally 0.05～15%, preferred 0.1～0.6%.

Temperature of reaction of the present invention is 40～120 ℃, is generally 50～100 ℃, preferred 60～90 ℃.

Reaction times of the present invention is 1～5 hour, preferred 1～3 hour.

Post-processing step main purpose of the present invention be remove desolvate, boiling point is lower than 180 ℃ material under the normal atmosphere such as lower alcohol, generally adopts the flash distillation aftertreatment technology to get final product, especially flash distillation half a hour at least more than 150 ℃ is favourable to improving product performance.If solid or spot are defective, can adopt and filter or the centrifugal impurity such as post-treating method removal bits that waits.

The sulphonate metal detergent turbidity that the present invention makes at last is generally less than 150JTU less than 200JTU.Not only when not influencing indexs such as sulfonate product metal content, can guarantee the turbidity of sulphonate metal detergent, and also improve the cleansing performance of sulphonate to a certain extent, reach the purpose of improving the sulfonate additive quality.

The method of improving quality of sulfonate detergent provided by the invention does not increase cost basically, and technology is simple, is convenient to transfer sky, and effect is remarkable, and suitability is strong.

Embodiment

For example the present invention is further specified through enforcement below, but be not limitation of the present invention, rights protection scope of the present invention is listed in claims.

Embodiment 1

Under the normal temperature, in the reaction flask that 1 liter band stirs, add 15 gram propyl carbinols, 3 gram methyl alcohol; 0.2 gram formic acid (purity 88%) stirs, then; With 100 gram solids contents is that 2% calcium sulfonate with high base number (Jinzhou company industrial goods) joins in the reaction flask, is heated to 60～65 ℃, reacts 1 hour; 80～90 ℃, reacted 1 hour, be flashed to 150 ℃, nitrogen gas is carried half a hour, and is last, adds 20 gram 10A super-cells (Changbai), after stirring, filters, and product test is row following table 1 as a result.

Comparative Examples 1

In the reaction flask that 1 liter band stirs, add solids content among the 100 gram embodiment 1 and be 2% calcium sulfonate with high base number (Jinzhou company industrial goods); After being heated to 150 ℃, add 20 gram 10A super-cells (Changbai), stir; Filter, product test is row following table 1 as a result.

Embodiment 2

Under the normal temperature, in the reaction flask that 1 liter band stirs, add 10 gram toluene, 3 gram methyl alcohol, 1.5 gram naphthenic acid; Stirring, then, is that 2% high base number calcium alkylbenzenesulfonate (Jinzhou company industrial goods) joins in the reaction flask with 100 gram solids, and reaction is 2 hours under 60～90 ℃ of temperature; Flash distillation, 150 ℃ of left and right sides nitrogen gas are carried half a hour, and are last, add 20 gram 10A super-cells (Changbai); Stir, filter, product test is row following table 1 as a result.

Comparative Examples 2

In the reaction flask that 1 liter band stirs, add solid among the 100 gram embodiment 2 and be 2% high base number calcium alkylbenzenesulfonate (Jinzhou company industrial goods); After being heated to 150 ℃, add 20 gram 10A super-cells (Changbai), stir; Filter, product test is row following table 1 as a result.

Embodiment 3

Under the normal temperature, in the reaction flask that 1 liter band stirs, add 12 gram toluene, 1 gram methyl alcohol; 0.1 gram formic acid (purity 88%) stirs, then; With 100 gram turbidity is that 165JTU, Mg content are that 9.6% overbased synthetic sulfonic acid magnesium (Jinzhou company industrial goods) joins in the reaction flask, is heated to 60～90 ℃, reacts 1 hour; Be flashed to 155 ℃, nitrogen gas is carried half a hour, and product test is row following table 2 as a result.

Embodiment 4

Under the normal temperature, in the reaction flask that 1 liter band stirs, add 8 gram propyl carbinols, 3 gram methyl alcohol; 0.1 gram formic acid (purity 88%) stirs, then; With 100 gram turbidity is that 387JTU, calcium contents are that 12.0% high base number calcium alkylbenzenesulfonate (Jinzhou company industrial goods) joins in the reaction flask, is heated to 60～90 ℃, reacts 1 hour; Be flashed to 150 ℃, nitrogen gas is carried half a hour, and product test is row following table 2 as a result.

Embodiment 5

Under the normal temperature, in the reaction flask that 1 liter band stirs, add 10 gram propyl carbinols, 3 gram methyl alcohol; 0.2 gram formic acid (purity 88%); Stirring, then, is that 468JTU, calcium contents are that 11.7% high base number calcium alkylbenzenesulfonate (Jinzhou company industrial goods) joins in the reaction flask with 100 gram turbidity; Be heated to 60～67 ℃, reacted 1 hour; 70～90 ℃, reacted 1 hour, be flashed to 155 ℃, nitrogen gas is carried half a hour, and product test is row following table 2 as a result.

Embodiment 6

Under the normal temperature, in the reaction flask that 1 liter band stirs, add 12 gram propyl carbinols, 3 gram methyl alcohol; 0.3 gram formic acid (purity 88%); Stirring, then, is that 785JTU, calcium contents are that 12.6% high base number calcium alkylbenzenesulfonate (Jinzhou company industrial goods) joins in the reaction flask with 100 gram turbidity; Be heated to 60～67 ℃, reacted 1 hour; 80～90 ℃, reacted 1 hour, be flashed to 155 ℃, nitrogen gas is carried half a hour, and product test is row following table 2 as a result.

Embodiment 7

Under the normal temperature, in the reaction flask that 1 liter band stirs, add 1 gram methyl alcohol, 0.1 gram formic acid (purity 88%); Stirring, then, is that 31JTU, calcium contents are that 2.6% low alkali value calcium sulphonate (Jinzhou company industrial goods) joins in the reaction flask with 100 gram turbidity; Be heated to 60～80 ℃, reacted 1 hour, be flashed to 155 ℃; Nitrogen gas is carried half a hour, and product test is row following table 2 as a result.

Table 1

Numbering	Turbidity JTU	Calcium contents %
			Embodiment 1	102	12.86
Comparative Examples 1	643	12.84
			Embodiment 2	116	12.78
Comparative Examples 2	＞800	12.92

Table 2

Table 1, table 2 presentation of results behind employing the present invention, when not influencing sulfonate product metal content index, can significantly reduce the turbidity index of sulphonate, and especially for the higher calcium sulfonate with high base number of turbidity, effect is extremely obvious.

Embodiment 8

With embodiment 4-A among the embodiment 4 and two kinds of high base number calcium alkylbenzenesulfonates of embodiment 4-B; Modulate the general oil of SF/CD level of 7.8% dosage and the CD level diesel engine oil of 6.0% dosage respectively; And carry out detergency evaluation, test result row following table 3 with reference to SHJ/T 0300-92 " crankcase (QZX) TP ".

Table 3

Embodiment 9

With embodiment 7-A among the embodiment 7 and two kinds of low alkali value calcium sulphonate of embodiment 7-B, carry out detergency evaluation, test result row following table 4 respectively by same recipe modulation two-stroke gasoline engine oil, and with reference to SHJ/T 0300-92 " crankcase (QZX) TP ".

Table 4

Table 3, table 4 presentation of results, the sulphonate that adopts the present invention to prepare can effectively reduce the coking amount of modulating oil product, improves the cleansing performance of sulphonate.

Claims

1. method of improving quality of sulfonate detergent is characterized in that: the sulphonate metal detergent is dissolved in the solvent, is 100% to add the C of 1～5% weight with sulphonate metal detergent weight _1～5The carboxylic acid of lower aliphatic alkanol and 0.1～0.6% weight after mixing, reacted 1～3 hour down at 60～90 ℃, through the distillation aftertreatment, can make the low turbidity sulphonate metal detergent of turbidity 150～200JTU; Solvent is that boiling point is lower than 150 ℃ aliphatic hydrocarbon, aromatic hydrocarbon or propyl carbinol under the normal atmosphere.

2. the sulphonate metal detergent method for quality of improving according to claim 1 is characterized in that: the sulphonate metal detergent is by comprising that mahogany acid or synthetic sulfonic acid and metal hydroxides or oxide compound are the basic metal or the alkaline earth metal sulfonate of feedstock production.

3. the sulphonate metal detergent method for quality of improving according to claim 2 is characterized in that: contain carbonate or borate in the sulphonate.

4. the sulphonate metal detergent method for quality of improving according to claim 1, it is characterized in that: solvent is hexane, heptane, benzene,toluene,xylene or propyl carbinol.

5. the sulphonate metal detergent method for quality of improving according to claim 1 is characterized in that: C _1～5The lower aliphatic alkanol is one or more mixtures in methyl alcohol, ethanol, Virahol, butanols, the amylalcohol.

6. the sulphonate metal detergent method for quality of improving according to claim 1, it is characterized in that: carboxylic acid is a formic acid.

7. the sulphonate metal detergent method for quality of improving according to claim 1 is characterized in that: flash distillation is adopted in the distillation aftertreatment.