CN101886013B - Method for preparing mixed-matrix metal cleaner - Google Patents
Method for preparing mixed-matrix metal cleaner Download PDFInfo
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Abstract
The invention relates to a method for preparing a mixed-matrix metal cleaner. In the method, naphthenic acid and alkyl salicylic acid are used as a mixed matrix, a hydrocarbon solvent is adopted, calcium hydroxide or calcium oxide is used as a calcifying reagent, methanol is used as an accelerator, a neutralization reaction is performed, an assistant is added, and 2 to 3 times of carbonation is performed to finally obtain a product. The metal cleaner prepared by the method of the invention has high comprehensive performance.
Description
Technical field
The present invention relates to a kind of preparation method of mixed-matrix metal cleaner, specifically, is the preparation method take naphthenic acid and alkyl salicylate as the metal detergent of mixed-matrix.
Background technology
Metal detergent is the main additive of I. C. engine oil, and it suppresses the generation of carbon distribution in the I. C. engine oil, paint film and greasy filth by neutralization, solubilising and dissemination, guarantees the normal operation of engine.Metal detergent mainly contains sulfonate, alkyl phenate, alkylsalicylate, sulfate-phosphate and naphthenate.
Highly basic calcium naphthenate has good oil soluble, acid neutralization capacity, water resisting property and diffusion, be the comparatively desirable binder component of marine cylinder oil, but the anti-oxidative stability of naphthenate is relatively poor.Alkylsalicylate has preferably antioxygen erosion resistance, but low temperature dispersity is not enough.
CN1239462C disclose a kind of alkaline alkyl salicylate the preparation method, the method is as raw material take organic carboxyl acid, add a certain amount of alkaline earth metal oxide or oxyhydroxide and carry out neutralization reaction, after question response is finished, add again alkyl salicylate and calcium hydroxide, in the presence of low mass molecule alcohol promotor, carry out carbonation reaction.The purpose of the method is to solve the alkaline alkyl salicylate with the composite compatible problem of alkylbenzene sulfonate, and the over-all properties of its product is also undesirable.
Mixed-matrix metal cleaner refers to that the mixture of two or more matrix and alkaline metal cpds react and the metal detergent that obtains.At present, it is that metal detergent, alkyl salicylate and the alkyl benzene sulphonate (ABS) of mixed-matrix is that metal detergent, alkylphenol and the alkylbenzene sulfonate of mixed-matrix is metal detergent of mixed-matrix etc. that the metal detergent of mixed-matrix has alkyl salicylate and alkylphenol, and the mixed-matrix metal cleaner take highly basic calcium naphthenate as host has no report.
Summary of the invention
The invention provides a kind of preparation method of mixed-matrix metal cleaner, a kind of preparation method take naphthenic acid and alkyl salicylate as the metal detergent of mixed-matrix particularly, the method not only can solve the composite compatibility problem of metal detergent, and can obtain the better product of over-all properties.
Among the present invention, all raw material consumptions are all take naphthenic acid weight as 100 parts.
Method provided by the present invention comprises:
(1) varsol, neutral oil, naphthenic acid, water, 20～150 parts alkyl salicylate, 10～100 parts methyl alcohol and 5～50 parts calcium hydroxide and/or calcium oxide mix, and carry out neutralization reaction;
(2) one or more in adding C1～C6 amine and the ammoniacal liquor, add-on is 10～100 parts;
(3) add 10～80 parts calcium hydroxide and/or calcium oxide, pass into carbonic acid gas and carry out carbonation reaction, the carbonic acid gas intake is 60～140% of theoretical value;
(4) step (3) is repeated 1～2 time;
(5) deviate from alcohol, water, solvent, promotor and solid residue after, obtain product.
Described varsol can be alkane, aromatic hydrocarbons or the mixture of the two, is preferably one or more in 60 ℃～180 ℃ straight-run spirit, benzene, toluene and dimethylbenzene of boiling range.The effect of solvent is the place that a reaction is provided for the reaction of neutralization reaction and high basicity.
Described neutral oil is kinematic viscosity (40 ℃) 10～50mm
2The lubricant base of/S; Be preferably 100SN or 150SN.The effect of neutral oil is the place that a stable dispersion is provided to final product.
The weight-average molecular weight of described naphthenic acid is 250～650, is preferably 300～500.
The carbon number of described alkyl salicylate is 8～30.
In the step (1), the consumption of solvent is preferably 50～600 parts, more preferably 200～500 parts; The consumption of neutral oil is preferably 50～200 parts, more preferably 50～150 parts; The consumption of water is preferably 10～70 parts, more preferably 20～50 parts; The consumption of methyl alcohol is preferably 35～85 parts; The consumption of calcium hydroxide and/or calcium oxide is preferably 10～40 parts; The consumption of alkylsalicylate is preferably 25～120 parts; Temperature of reaction is preferably 45～60 ℃; Reaction times is preferably 30～90min.
Add one or more in C1～C6 amine and the ammoniacal liquor in the step (2), add-on is preferably 20～80 parts.
In the step (2), described C1～C6 amine is preferably quadrol, propylene diamine or hexanediamine.
Step also can add alkali metal chloride and/or alkaline earth metal chloride in (2), in preferred sodium-chlor, Repone K, magnesium chloride and the calcium chloride one or more.The consumption of alkali metal chloride and/or alkaline earth metal chloride is 1～15 part, is preferably 4～10 parts.Adding alkali metal chloride and/or alkaline earth metal chloride help avoid owing to carbonic acid gas is excessive and produce precipitation, and the terminal point control of carbonation reaction is more prone to.
Described calcium hydroxide and/or calcium oxide both can be analytical pure, also can be technical pures.
Theoretical value in the step (3) is calculated and is got with the calcium hydroxide amount of each adding.
In the step (3), the speed that passes into of carbonic acid gas is preferably 0.5～2.0ml/ming.
The consumption of calcium hydroxide and/or calcium oxide is preferably 20～60 parts in the step (3).
In the step (3), the temperature of carbonation reaction is preferably 45～60 ℃.
The present invention has following useful technique effect:
(1) adopt the prepared metal detergent of the inventive method to have good over-all properties.Have good high temperature detergency, low temperature dispersity and anti-oxidative stability with the resulting metal detergent of the inventive method, and have excellent consistency.
(2) the present invention has formed novel metal detergent colloidal structure, thereby makes metal detergent have better stability.
(3) the present invention is more prone to the terminal point control of carbonation reaction by adding alkali metal chloride and/or alkaline earth metal chloride.
Embodiment
Further set forth by the following examples the present invention.
The present invention adopts coking, lacquering plate test evaluation high temperature detergent performance, low temperature spot test evaluation low energy dispersion, oxide thin layer test, PDSC test evaluation antioxygen property.
(1) coke test
The formation testing of certain temperature is splashed the high temperature surface of aluminum plate in for some time interval, rebake for some time, in the regulation test period, repeating two processes, according to formation testing in surface of aluminum plate because the sedimental weight of the burnt shape that produces of thermooxidizing is estimated the high temperature coking tendency of formation testing, estimate thus thermal oxidation stability and the high temperature detergency of formation testing.
Experiment condition: test oil 260g, motor rotary speed 1000rpm, 320 ℃ of aluminium sheet temperature, 100 ℃ of formation testing temperature are spattered oil time 15S, storing time 45S, test period 2h.
(2) low energy dispersion evaluation
Utilize carbon black as disperseing parent, investigate oil sample dispersive ability to external contaminant under cold condition.The 19.5g formation testing is mixed high-speed stirring 10min with 0.5g carbon black ointment; Be under the condition of 14A at constant current with ultrasonic wave again, vibration 5min leaves standstill 18h with sample in 50 ℃ of baking ovens; Drip on industrial filter paper after taking out, drop mass is controlled between 0.020～0.025g, leaves standstill 2h in 50 ℃ of baking ovens, measures diffusion circle diameter (d) and scraper ring diameter (D).Ratio γ=d/D * 100 are as the measurement index of dispersive ability quality.
(3) oxidation stability evaluation
Adopt the Dupont2100 thermal analyzer, measure oxidation induction period, investigate oil oxidation stability.
Test conditions: oxygen gas flow rate 50ml/min, oil sample 1～2mg, 50 ℃/min of heat-up rate, 180 ℃ of steady temperatures.
(4) consistency experiment
Get each 3 gram of two kinds of additives, be dissolved in the 50 gram base oils, and with 500 ± 50 rev/mins of stirrings 15 minutes, mix, 100 ℃ of lower placements 96 hours, measure the precipitation capacity that produces.
Embodiment 1
In reactor, add 150 milliliters of 120# industrial napthas, 150SN neutral oil 35 grams, water 12 grams, methyl alcohol 20 grams, calcium hydroxide 10 grams, naphthenic acid raw material 40 gram (pure acid number 118mgKOH/g, acid content 72%), alkyl salicylate 25 grams, the control temperature of reaction is at 45-60 ℃ after adding, behind the neutralization reaction 60min, generate neutral calcium naphthenate and alkyl sodium salicylate.Add 15 gram calcium hydroxides, 20 gram quadrols pass into carbonic acid gas, Ventilation Rate about 80ml/min, intake reach theoretical value 70% the time, add 15 gram calcium hydroxides, pass into carbonic acid gas and carry out the secondary carbonation reaction, when the specific absorption of carbonic acid gas reached 80%, reaction finished.Carbonating is warmed up to 120 ℃ of dealcoholysis, water after finishing.Add 100 milliliters of gasoline in the material that obtains, then put into whizzer, 4000rpm is centrifugal with rotating speed, flash distillation thing after centrifugal is put into matrass with decompression facility, at first be warmed up to 120 ℃ of air distillations, 5 ℃/min of heat-up rate, constant temperature 30min, then carry out underpressure distillation to system, vacuum degree control is more than 0.02Mpa.Temperature is controlled at 150 ℃, and constant temperature 30min obtains product at last.
Embodiment 2
In reactor, add 150 milliliters of 120# industrial napthas, 150SN neutral oil 35 grams, water 11 grams, methyl alcohol 20 grams, calcium hydroxide 10 grams, naphthenic acid raw material 50 gram (pure acid number 118mgKOH/g, acid content 72%), alkyl salicylate 15 grams, the control temperature of reaction is at 45～60 ℃ after adding, behind the neutralization reaction 60min, generate neutral calcium naphthenate and alkyl sodium salicylate.Add 15 gram calcium hydroxides, 20 gram quadrols, the NaCl aqueous solution of 4 gram 25wt%, pass into carbonic acid gas, Ventilation Rate about 80ml/min, intake reach theoretical value 70% the time, add 15 gram calcium hydroxides, pass into carbonic acid gas and carry out the secondary carbonation reaction, when the specific absorption of carbonic acid gas reached 80%, reaction finished.Carbonating is warmed up to 120 ℃ of dealcoholysis, water after finishing.Add 100 milliliters of gasoline in the material that obtains, then put into whizzer, 4000rpm is centrifugal with rotating speed, flash distillation thing after centrifugal is put into matrass with decompression facility, at first be warmed up to 120 ℃ of air distillations, 5 ℃/min of heat-up rate, constant temperature 30min, then carry out underpressure distillation to system, vacuum degree control is more than 0.02Mpa.Temperature is controlled at 150 ℃, and constant temperature 30min obtains product at last.
Embodiment 3
In reactor, add 150 milliliters of 120# industrial napthas, 150SN neutral oil 35 grams, water 12 grams, methyl alcohol 20 grams, calcium hydroxide 10 grams, naphthenic acid raw material 35 gram (pure acid number 118mgKOH/g, acid content 72%), alkyl salicylate 30 grams, the control temperature of reaction is at 45～60 ℃ after adding, behind the neutralization reaction 60min, generate neutral calcium naphthenate and alkyl sodium salicylate.Add 15 gram calcium hydroxides, 10 gram quadrols pass into carbonic acid gas, Ventilation Rate about 80ml/min, intake reach theoretical value 70% the time, add 15 gram calcium hydroxides, pass into carbonic acid gas and carry out the secondary carbonation reaction, when the specific absorption of carbonic acid gas reached 80%, reaction finished.Carbonating is warmed up to 120 ℃ of dealcoholysis, water after finishing.Add 100 milliliters of gasoline in the material that obtains, then put into whizzer, 4000rpm is centrifugal with rotating speed, flash distillation thing after centrifugal is put into matrass with decompression facility, at first be warmed up to 120 ℃ of air distillations, 5 ℃/min of heat-up rate, constant temperature 30min, then carry out underpressure distillation to system, vacuum degree control is more than 0.02Mpa.Temperature is controlled at 150 ℃, and constant temperature 30min obtains product at last.
Products obtained therefrom is called in (base oil is comprised of 500SN and 150BS) in the base oil by the single dose of 3wt%, carry out the evaluation of high temperature detergency, low temperature dispersity and Oxidation Stability, and compare with T114 (calcium naphthenate) and T109 (alkyl sodium salicylate).The results are shown in Table 1.
Table 1
Table 1 can be found out, the mixed-matrix metal cleaner that the inventive method is synthetic has good detergent-dispersant performance, low temperature dispersity, anti-oxidative stability and excellent compatibility performance, is the comprehensive metal detergent of a kind of performance.
Claims (18)
1. the preparation method of a mixed-matrix metal cleaner comprises:
(1) varsol, neutral oil, naphthenic acid, 10～70 parts water, 20～150 parts alkyl salicylate, 10～100 parts methyl alcohol and 5～50 parts calcium hydroxide and/or calcium oxide mix, and carry out neutralization reaction;
(2) one or more in adding C1～C6 amine and the ammoniacal liquor, add-on is 10～100 parts;
(3) add 10～80 parts calcium hydroxide and/or calcium oxide, pass into carbonic acid gas and carry out carbonation reaction, the carbonic acid gas intake is 60～140% of theoretical value;
(4) step (3) is repeated 1～2 time;
(5) deviate from alcohol, water, solvent, promotor and solid residue after, obtain product;
Wherein, the raw material consumption is take naphthenic acid weight as 100 parts.
2. in accordance with the method for claim 1, it is characterized in that described varsol is one or more in 60～180 ℃ straight-run spirit, benzene, toluene and dimethylbenzene of boiling range.
3. in accordance with the method for claim 1, it is characterized in that described neutral oil is 100SN or 150SN.
4. in accordance with the method for claim 1, it is characterized in that the weight-average molecular weight of described naphthenic acid is 250～650.
5. in accordance with the method for claim 1, it is characterized in that the carbon number of described alkyl salicylate is 8～30.
6. in accordance with the method for claim 1, it is characterized in that in the step (1), the consumption of solvent is 50～600 parts, the consumption of neutral oil is 50～200 parts.
7. in accordance with the method for claim 1, it is characterized in that in the step (1), the consumption of water is 20～50 parts.
8. in accordance with the method for claim 1, it is characterized in that in the step (1), the consumption of methyl alcohol is 35～85 parts.
9. in accordance with the method for claim 1, it is characterized in that in the step (1), the consumption of calcium hydroxide and/or calcium oxide is 10～40 parts.
10. in accordance with the method for claim 1, it is characterized in that in the step (1), the consumption of alkylsalicylate is preferably 25～120 parts.
11. in accordance with the method for claim 1, it is characterized in that in the step (1), temperature of reaction is 45～60 ℃; Reaction times is 30～90min.
12. in accordance with the method for claim 1, it is characterized in that, add alkali metal chloride and/or alkaline earth metal chloride in the step (2).
13. in accordance with the method for claim 12, it is characterized in that the consumption of alkali metal chloride and/or alkaline earth metal chloride is 1～15 part.
14. in accordance with the method for claim 13, it is characterized in that the consumption of alkali metal chloride and/or alkaline earth metal chloride is 4～10 parts.
15. in accordance with the method for claim 1, it is characterized in that the C1 in the step (2)～C6 amine is quadrol, propylene diamine or hexanediamine.
16. in accordance with the method for claim 1, it is characterized in that the consumption of calcium hydroxide and/or calcium oxide is 20～60 parts in the step (3).
17. in accordance with the method for claim 1, it is characterized in that in the step (3), the temperature of carbonation reaction is 45～60 ℃.
18. according to the prepared metal detergent of either method in the claim 1～17.
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| CN101886013B true CN101886013B (en) | 2013-01-30 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102477341A (en) * | 2010-11-23 | 2012-05-30 | 中国石油天然气股份有限公司 | Method for preparing low ash engine oil metal detergent |
| WO2012087775A1 (en) * | 2010-12-21 | 2012-06-28 | The Lubrizol Corporation | Lubricating composition containing a detergent |
| CN103131520A (en) * | 2011-11-25 | 2013-06-05 | 中国石油天然气股份有限公司 | Metal detergent accelerant, preparation and applications thereof |
| SG11201503870SA (en) * | 2012-12-17 | 2015-06-29 | Lubrizol Corp | Process for producing an overbased metal detergent |
| CN116478748A (en) * | 2022-01-13 | 2023-07-25 | 中国石油天然气股份有限公司 | Preparation method of neutral salicylate detergent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1377944A (en) * | 2002-03-07 | 2002-11-06 | 中国石油天然气股份有限公司 | Process for preparing compound metal type lubricating oil cleaning agent |
| CN1465560A (en) * | 2002-06-28 | 2004-01-07 | 中国石油天然气股份有限公司 | Process for preparing ultrahigh basicity calcium naphthenate |
| CN1504451A (en) * | 2002-11-29 | 2004-06-16 | 中国石油天然气股份有限公司 | Novel preparing process for alkalinous alkyl salicylate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1523540B1 (en) * | 2002-07-23 | 2012-11-14 | Chemtura Canada Co./Cie | Engine oil comprising overbased salicylates based on styrenated salicylic acid |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1377944A (en) * | 2002-03-07 | 2002-11-06 | 中国石油天然气股份有限公司 | Process for preparing compound metal type lubricating oil cleaning agent |
| CN1465560A (en) * | 2002-06-28 | 2004-01-07 | 中国石油天然气股份有限公司 | Process for preparing ultrahigh basicity calcium naphthenate |
| CN1504451A (en) * | 2002-11-29 | 2004-06-16 | 中国石油天然气股份有限公司 | Novel preparing process for alkalinous alkyl salicylate |
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