CN104099155A - Preparation method of high-extreme pressure resistance calcium sulfonate - Google Patents
Preparation method of high-extreme pressure resistance calcium sulfonate Download PDFInfo
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- CN104099155A CN104099155A CN201310114080.9A CN201310114080A CN104099155A CN 104099155 A CN104099155 A CN 104099155A CN 201310114080 A CN201310114080 A CN 201310114080A CN 104099155 A CN104099155 A CN 104099155A
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Abstract
The invention discloses a preparation method of high-extreme pressure resistance calcium sulfonate. According to exploration and research on a calcium alkylbenzene sulfonate additive production technology, alkyl benzene sulfonic acid, a calcium salt and an alkaline compound of calcium are used as raw materials and through a specific solvent system and technical conditions, a product structure is effectively controlled and product extreme pressure resistance is fully improved. 2-5% of the high-extreme pressure resistance calcium sulfonate is added into base oil, can effectively improve oil product sintering load by 2-3 times and can realize oil product sintering load 1.2-1.6 times that of the common calcium sulfonate additive. The high-extreme pressure resistance calcium sulfonate as an additive can be widely used in high-quality internal combustion engine oil, industrial oil and lubricating grease products.
Description
(1) technical field
The present invention relates to a kind of preparation method of high extreme pressure property calcium sulphonate, this additive can be widely used in high-grade I. C. engine oil, industry oil and grease product.Belong to lubricant additive field.
(2) background technology
Along with the continuous enhancing of people's environmental protection consciousness, environmental regulation constantly impels lubricant more clean.The application of high-sulfur, high phosphorus extreme pressure agent is being subject to increasing restriction.The lubricant additive of exploitation environmental protection, high energy, multiple-effect has become development trend.Traditional sulfonic acid calcium salt itself has certain extreme pressure property, what wherein have extreme pressure effect is calcium carbonate granule (micelle) contained in product, calcium carbonate generally exists with amorphous form, himself abrasion resistance is limited, yet when in calcium sulphonate product, contained calcium carbonate is crystal type (hereinafter to be referred as crystal type calcium sulphonate), the extreme pressure property of product can significantly strengthen, and shows outstanding synergistic effect during particularly with the composite use of part extreme pressure anti-wear additives.
Research shows, it is relevant that the protective membrane that physical deposition forms occurs on friction surface for calcium sulphonate tribological property and its calcium carbonate granule.In friction process, due to the desorption of surface stabilizer, make calcium carbonate granule out exposed, at friction surface, a large amount of depositions occur, form deposition protective membrane.Compare with traditional calcium sulphonate product, in crystal type calcium sulphonate, the sequence that is arranged with of calcium carbonate molecule more strengthens, product micella molecular change is large, and in friction process, these regularly arranged calcium carbonate deposit effectively in a large number at surface of friction pair, thereby the extreme pressure property of product is significantly strengthened.
In crystal type calcium sulphonate, it is large that the radius of calcium carbonate particles becomes, and micella molecular expansion be difficult to form stable colloidal structure and be scattered in oil, thereby it is very difficult directly to prepare crystal type calcium sulphonate product, there is not yet at present relevant report both at home and abroad.Patent US6107259 has reported a kind of indirectly synthetic method, with calcium sulfonate with high base number additive raw material, add C1-C5 alkyl alcohol, water, varsol etc. to mix, under 65 ℃ of-70 ℃ of conditions, add dispersion agent and transforming agent to transform, finally by processing and obtain crystal type calcium sulphonate product later.The relative complex process of the method, and product performance affected by material performance larger, are difficult to adjust calcium carbonate content and base oil in product and form, thereby range of application and product performance are received larger restriction.
Technique of the present invention is to take alkyl benzene sulphonate (ABS) as raw material, obtains crystal type calcium sulphonate product under particular promoter, Ventilation Rate, aeration time, specific solvent systems condition.Compared with the prior art, technique of the present invention is simple, can effectively reduce production costs, and can be widely used in multiple lubricant product.
(3) summary of the invention
The present invention relates to a kind of crystal type calcium sulphonate of stable performance, product feature is that glue core calcium carbonate exists and is scattered in oil product with colloidal form with crystal type form.This product has the use propertieies such as good high temperature detergency, hot storage stability, extreme pressure anti-wear, is a kind of lubricating oil/fat additives of superior performance.
The object of the invention is to provide the preparation method of this additive.It is initial feed that the method be take alkyl benzene sulphonate (ABS), calcium oxide (or calcium hydroxide) etc., introducing under the condition that alcohol compound is promotor, with a certain proportion of ratio of components, through metallization reaction and high basicity reaction, prepare crystal type calcium sulphonate additive product.Preparation process is as follows:
In the reactor with electric mixer, thermometer and condensation water trap of appointment, add quantitative calcium oxide, calcium chloride, alcohols promotor and solvent compositions, and open reaction stirrer, the alkyl benzene sulphonate (ABS), tensio-active agent and the base oil that add again metering, be warming up to 40 ℃-90 ℃, carry out metallization reaction, keep temperature of reaction 0.5-4.0 hour.Then pass into the carbon dioxide of particular flow rate, carry out high basicity reaction, sustained reaction 1.0-4.0 hour.Continue to be warming up to 110 ℃-150 ℃, remove water and alcohols promotor in system.Finally cooling, solubilizing agent dilution, centrifugal, remove the gred, remove under reduced pressure solvent, obtain product.
In metallization and high basicity reaction, promotor is used methyl alcohol (chemical reagent or industrial goods), ethylene glycol, Virahol, Pentyl alcohol or its homologue (chemical reagent or industrial goods), the ratio of components of each component has certain ratio, in 100.0 parts of (weight) alkyl benzene sulphonate (ABS)s, in metallization reaction, thinning oil is 80.0-130.0 part, calcium oxide is 50.0-85.0 part, calcium chloride is 0.8-2.5 part, alcohols promotor is 90.0-150.0 part, tensio-active agent is 15.0-25.0 part, solvent compositions 100.0-240.0 part, reaction completes under normal pressure, 40 ℃-90 ℃ of temperature, reaction 0.5-4.0 hour.Maintain afterwards temperature of reaction constant, pass into 50.0-110.0 part carbonic acid gas and carry out high basicity reaction under normal pressure, carbon dioxide flow is 10L/hKg-20L/hKg, reaction times 1.0-4.0 hour.This reaction system can be applicable to different stage calcium oxide, and sintetics has excellent extreme pressure anti-wear and stability.
Tensio-active agent used can be alkyl salicylate, polyisobutylene butanedioic anhydride or its homologue, alkylphenol, alkenyl succinic acid, oleic acid, SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER etc.
Thinning oil can be dissimilar lubricant base, as other base oils of different viscosity level such as I class, II class, III classes, or the dissimilar base oil such as paraffinic base, cycloalkyl and hydrogenation.
Described alkyl benzene sulphonate (ABS) can be C for chain length
18-26linear alkyl benzene sulfonate, heavy alkylbenzene sulfonic acid or its composition.
The high base number crystal type calcium sulphonate additive of preparing by the inventive method, its ft-ir characteristic absorption peak is 878cm
-1, and common calcium sulphonate product infrared absorption peak is 862cm
-1.From document, structure and the T106 calcium sulphonate product of crystal type calcium sulphonate product are basically identical, and in infrared spectra, the position of other absorption peak is identical, and only the absorption peak position of calcium carbonate is different, and the absorption peak position of crystal type calcium carbonate is at 877cm
-1, and in common T106 calcium sulphonate product the absorption peak position of calcium carbonate at 862cm
-1.Product of the present invention is under identical base number condition, and extreme pressure property is improved largely than common calcium sulphonate product, and product is widely used in high-grade I. C. engine oil, industry oil and grease product.Will produce good social benefit and economic benefit.
The extreme pressure and antiwear behavior of crystal type calcium sulphonate, thermal stability evaluation result are in Table 1.
The assessment of performance result of table 1 crystal type calcium sulphonate product
(4) embodiment
The following examples are to further illustrate of the present invention, rather than limit the invention, and spirit of the present invention and protection domain are listed in claims.
Below in embodiment solvent for use composition proportioning in Table 2.
Table 2 solvent compositions proportioning
| Solvent title | Solvent compositions 1 | Solvent compositions 2 | Solvent compositions 3 |
| Straight-run spirit (g) | 200 | 70 | 200 |
| Toluene (g) | ? | 130 | ? |
| Water (g) | 8 | 8 | 10 |
Embodiment 1
Will be with electric mixer, thermometer, the four-hole boiling flask of the 1000mL of condensation water trap installs, drop into 58.0 grams of calcium oxide, 1.2 grams of calcium chloride, solvent compositions 1, 95.0 gram methyl alcohol, open and stir, add 120.0 grams of alkyl benzene sulphonate (ABS)s, 20.0 gram alkyl salicylate, 80.0 grams of base oil HVI400, be warming up to 45-55 ℃, after approximately 1 hour, pass into afterwards carbon dioxide (controlling gas velocity is 150 ml/min) and carry out high basicity reaction 2.0 hours, after reaction finishes, be warming up to 110 ℃, except anhydrating and promotor methyl alcohol, solubilizing agent dilution, cooling rear centrifugal, (210 ℃ of supernatant liquid underpressure distillation, 3KPa) steam and desolventize to obtain product, product base number is 292mgKOH/g, Ca% is 11.80, ft-ir characteristic absorption peak is 878cm
-1.
Embodiment 2
Will be with electric mixer, thermometer, the four-hole boiling flask of the 1000mL of condensation water trap installs, drop into 58.0 grams of calcium oxide, 1.2 grams of calcium chloride, solvent compositions 2, 95.0 gram Virahol, open and stir, add 120.0 grams of alkyl benzene sulphonate (ABS)s, 20.0 gram alkyl salicylate, 80.0 grams of base oil HVI400, be warming up to 45-55 ℃, after approximately 1 hour, pass into afterwards carbon dioxide (controlling gas velocity is 150 ml/min) and carry out high basicity reaction 2.0 hours, after reaction finishes, be warming up to 110 ℃, except anhydrating and promotor Virahol, solubilizing agent dilution, cooling rear centrifugal, (210 ℃ of supernatant liquid underpressure distillation, 3KPa) steam and desolventize to obtain product, product base number is 304mgKOH/g, Ca% is 11.96, ft-ir characteristic absorption peak is 878cm
-1.
Embodiment 3
Will be with electric mixer, thermometer, the four-hole boiling flask of the 1000mL of condensation water trap installs, drop into 58.0 grams of calcium oxide, 1.2 grams of calcium chloride, solvent compositions 3, 120.0 grams of Virahols, open and stir, add 120.0 grams of alkyl benzene sulphonate (ABS)s, 20.0 gram alkyl salicylate, 80.0 grams of base oil HVI400, be warming up to 45-55 ℃, after approximately 1 hour, pass into afterwards carbon dioxide (controlling gas velocity is 100 ml/min) and carry out high basicity reaction 2.5 hours, after reaction finishes, be warming up to 110 ℃, except anhydrating and promotor Virahol, solubilizing agent dilution, cooling rear centrifugal, (210 ℃ of supernatant liquid underpressure distillation, 3KPa) steam and desolventize to obtain product, product base number is 304mgKOH/g, Ca% is 12.32, ft-ir characteristic absorption peak is 878cm
-1.
Embodiment 4
Will be with electric mixer, thermometer, the four-hole boiling flask of the 1000mL of condensation water trap installs, drop into 58.0 grams of calcium oxide, 1.2 grams of calcium chloride, solvent compositions 3, 120.0 grams of methyl alcohol, open and stir, add 120.0 grams of alkyl benzene sulphonate (ABS)s, 20.0 gram alkenyl succinic acid, 80.0 grams of base oil HVI400, be warming up to 45-55 ℃, after approximately 1 hour, pass into afterwards carbon dioxide (controlling gas velocity is 100 ml/min) and carry out high basicity reaction 2.3 hours, after reaction finishes, be warming up to 110 ℃, except anhydrating and promotor methyl alcohol, solubilizing agent dilution, cooling rear centrifugal, (210 ℃ of supernatant liquid underpressure distillation, 3KPa) steam and desolventize to obtain product, product base number is 310mgKOH/g, Ca% is 12.51, ft-ir characteristic absorption peak is 878cm
-1.
Claims (8)
1. the preparation method of a high extreme pressure property calcium sulphonate, it is characterized in that: to appointment with electric mixer, in the reactor of thermometer and condensation water trap, add quantitative calcium oxide, calcium chloride, alcohols promotor and solvent compositions, and open reaction stirrer, the alkyl benzene sulphonate (ABS) that adds again metering, tensio-active agent and base oil, be warming up to 40 ℃-90 ℃, keep temperature of reaction 0.5-4.0 hour, then pass into the carbon dioxide of particular flow rate, sustained reaction 1.0-4.0 hour, continue to be warming up to 110 ℃-150 ℃, remove water and alcohols promotor in system, finally cooling, solubilizing agent dilution, centrifugal, slagging-off, remove solvent under reduced pressure, obtain product.
2. a kind of preparation method of high extreme pressure property calcium sulphonate according to claim 1, it is characterized in that: the ratio of components of each component has certain ratio, in 100.0 parts of (weight) alkyl benzene sulphonate (ABS)s, in metallization reaction, thinning oil is 80.0-130.0 part, calcium oxide is 50.0-85.0 part, calcium chloride is 0.8-2.5 part, alcohols promotor is 90.0-150.0 part, tensio-active agent is 15.0-25.0 part, solvent compositions 100.0-240.0 part, passes into 50.0-110.0 part carbonic acid gas in high basicity reaction and reacts.
3. a kind of preparation method of high extreme pressure property calcium sulphonate according to claim 1, is characterized in that: described solvent compositions is two or more mixtures of gasoline, solvent oil, toluene, dimethylbenzene and water.
4. a kind of preparation method of high extreme pressure property calcium sulphonate according to claim 1, is characterized in that: described carbon dioxide flow is 10L/hKg-20L/hKg.
5. a kind of preparation method of high extreme pressure property calcium sulphonate according to claim 1, is characterized in that: described alkyl benzene sulphonate (ABS) is that chain length is C
18-26linear alkyl benzene sulfonate, heavy alkylbenzene sulfonic acid or its composition.
6. a kind of preparation method of high extreme pressure property calcium sulphonate according to claim 1, is characterized in that: described alcohols promotor is methyl alcohol, ethylene glycol, Virahol, Pentyl alcohol.
7. a kind of preparation method of high extreme pressure property calcium sulphonate according to claim 1, is characterized in that: described tensio-active agent is alkyl salicylate, polyisobutylene butanedioic anhydride or its homologue, alkylphenol, alkenyl succinic acid, oleic acid, SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER.
8. a kind of preparation method of high extreme pressure property calcium sulphonate according to claim 1, is characterized in that: described base oil is I class, II class, III class base oil or its composition.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106520264A (en) * | 2015-09-11 | 2017-03-22 | 中国石油天然气股份有限公司 | Preparation method of mixed detergent |
| CN106590814A (en) * | 2016-12-05 | 2017-04-26 | 新乡市瑞丰新材料股份有限公司 | Preparation method of composite calcium sulfonate grease |
| CN111234908A (en) * | 2020-03-16 | 2020-06-05 | 杭州埃力普新能源科技有限公司 | Environment-friendly warm pier oil and preparation method thereof |
| CN113249162A (en) * | 2021-05-24 | 2021-08-13 | 新乡市瑞丰新材料股份有限公司 | Preparation method of composite calcium sulfonate antirust agent |
| CN115247091A (en) * | 2021-04-28 | 2022-10-28 | 中国石油天然气股份有限公司 | Composite type cleaning dispersant and preparation method thereof |
| CN116478749A (en) * | 2022-01-14 | 2023-07-25 | 中国石油天然气股份有限公司 | Preparation method of ultrahigh-base-number calcium sulfonate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101318916A (en) * | 2008-06-20 | 2008-12-10 | 辽宁天合精细化工股份有限公司 | Method for preparing high-alkali value (TBN300) synthesized calcium alkyl benzene sulfonate |
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2013
- 2013-04-03 CN CN201310114080.9A patent/CN104099155B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101318916A (en) * | 2008-06-20 | 2008-12-10 | 辽宁天合精细化工股份有限公司 | Method for preparing high-alkali value (TBN300) synthesized calcium alkyl benzene sulfonate |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106520264A (en) * | 2015-09-11 | 2017-03-22 | 中国石油天然气股份有限公司 | Preparation method of mixed detergent |
| CN106590814A (en) * | 2016-12-05 | 2017-04-26 | 新乡市瑞丰新材料股份有限公司 | Preparation method of composite calcium sulfonate grease |
| CN106590814B (en) * | 2016-12-05 | 2019-11-19 | 新乡市瑞丰新材料股份有限公司 | A kind of preparation method of calcium sulfonate complex grease |
| CN111234908A (en) * | 2020-03-16 | 2020-06-05 | 杭州埃力普新能源科技有限公司 | Environment-friendly warm pier oil and preparation method thereof |
| CN115247091A (en) * | 2021-04-28 | 2022-10-28 | 中国石油天然气股份有限公司 | Composite type cleaning dispersant and preparation method thereof |
| CN113249162A (en) * | 2021-05-24 | 2021-08-13 | 新乡市瑞丰新材料股份有限公司 | Preparation method of composite calcium sulfonate antirust agent |
| CN116478749A (en) * | 2022-01-14 | 2023-07-25 | 中国石油天然气股份有限公司 | Preparation method of ultrahigh-base-number calcium sulfonate |
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