A kind of preparation method of ultrahigh-basicity composite metal detergent
The present invention relates to a kind of overbased preparation process lubricant oil additive, especially a kind of preparation method of ultrahigh-basicity composite metal detergent belongs to the lubricating oil field.
As everyone knows, lubricant oil metal detergent is mainly used in the engine oil, it can suppress the generation that oil ageing is gone bad or reduced the surperficial high temperature deposition thing of piston land (piston, piston ring, cylinder sleeve, annular groove) under hot conditions, make engine interior (combustion chamber and crankcase) keep peace and quiet.Metal detergent generally by carbonate (or borate) be adsorbed on the oil solution that stable load micelle that the lip-deep tensio-active agent of carbonate (or borate) forms and free surfactant molecule and micella thereof are constituted, it mainly comprises alkylbenzene sulfonate, alkyl monosulfide phenates, alkylsalicylate, sulfate-phosphate etc.Alkylsalicylate (calcium, magnesium) has obtained using widely as the used main additive of I. C. engine oil, wherein mainly comprises the calcium salt product of basic, normal, high base number.In recent years, along with save energy and more and more strictness of environmental protection requirement, engine design develops to miniaturization, high-power, high-speed direction day by day, and therefore the high temperature detergent performance to oil product has proposed more and more harsher requirement.Overbased metal detergent product also has good performances such as thermostability except that having fabulous high temperature detergent performance, will be widely used in the top-grade lubricating oil, especially in base number higher bunker oil and railroad engines oil.Owing to have high base number, thereby can reduce the add-on of additive in oil product significantly.It is more that relevant overbased sulfonate production prepares patent, but the patented technology of relevant ultrahigh basicity alkyl salicylate seldom is seen in report, only having at present with methyl alcohol is promotor, once metallized preparation technology is seen in report, but synthetic product under this technology is unsatisfactory with the consistency of sulfonate; In the patent No. is in the patent of CN94106385.2, though can see and when the preparation alkyl sodium salicylate, introduce tensio-active agent, solved the compatibility problem of two big class purification agents, but be a metallization process, and basicity alkyl calcium salicylate product in only obtaining can not satisfy the high alkalinity requirement of oil product.
The objective of the invention is to provide a kind of based on alkyl salicylate, under the condition of introducing secondary accelerator and tensio-active agent, prepare ultrahigh-basicity composite calcium salt metal detergent by the secondary metals metallization processes, this product not only contains a certain amount of alkylsalicylate, alkylbenzene sulfonate, but also contain a spot of alkyl phenate, thereby except that every performance with traditional ultrahigh basicity alkyl calcium salicylate, particularly the consistency with sulfonate has had very big improvement, thereby can be the new additive agent that lubricating oil provides a kind of compatibility performance, favorable dispersity.
The preparation method of a kind of ultrahigh-basicity composite metal detergent calcium salt of the present invention, promptly introduce tensio-active agent and two single metal metallization processes are as follows: the gasoline (industrial goods) and the methyl alcohol (industrial goods) that in there-necked flask, drop into metering, be warming up to 30-60 ℃, drop into the industrial calcium oxide (purity is more than 93%) of metering, the water that adds metering simultaneously, observe mixture retrogradation gradually in the flask, and be attended by the temperature rise phenomenon.Stir after 30 minutes, add the alkyl salicylate of metering and specific tensio-active agent alkyl benzene sulphonate (ABS), stirring reaction is kept temperature of reaction 40-60 ℃, carries out neutralization reaction 1 hour.Thereafter add metered calcium oxide, methyl alcohol and Ammonia secondary accelerator, under 40-60 ℃, keep reaction 30 minutes, feed a certain amount of carbon dioxide then, carry out high basicity reaction 2 hours.After reacting end, be warming up to 110 ℃, steaming engaging benzenemethanol and water dilute the decompression of centrifugal back and steam desolventizing, get product.Promotor is used methyl alcohol, and secondary accelerator uses ammonia and ammonium salt, and tensio-active agent is an alkyl benzene sulphonate (ABS), and the ratio of components of each component has certain ratio.In 90 parts of (weight) alkyl salicylates (about oil-containing 40%), tensio-active agent is 1-60 part, calcium oxide is 25-35 part, methyl alcohol is 30-150 part, water is 6.0-13.0 part, and the Ammonia secondary accelerator is 1.0-10.0 part, and solvent is 40-200 part, carbonic acid gas is 20-100 part, and temperature of reaction is controlled between 40-60 ℃.Tensio-active agent is two alkyl or monoalkylated benzenes sulfonic acid, and this reaction system can be fit to the calcium oxide of different stage, and reaction can be that boiling range is 60-160 ℃ a straight-run spirit with solvent, also can be that boiling point is higher than 120 ℃ material, as dimethylbenzene.The structure of reacting used main raw material alkyl salicylate is:
Wherein R is C
8-30Alkyl chain.Methyl alcohol must be purity greater than 95% chemical reagent or industrial goods, and secondary accelerator can be Ammonia products such as ammoniacal liquor, volatile salt or bicarbonate of ammonia, preferably selects chemical pure bicarbonate of ammonia for use.Tensio-active agent, methyl alcohol, the water yield and secondary accelerator are the principal elements that influences product base number and viscosity.The appropriate surfactant consumption is 2.0-50.0 gram/90 gram alkyl salicylates, and methanol usage is 60-150 gram/90 gram alkyl salicylates; The consumption of suitable water is 7.0-12.0 gram/90.0 gram alkyl salicylates.Sintetics has excellent anti-oxidant anticorrosive, thermally-stabilised, consistency and detergent-dispersant performance energy.
In the synthetic reaction process of ultrahigh-basicity composite metal detergent calcium salt product of the present invention:
The effect of methyl alcohol: methyl alcohol is as the carrier of inorganic phase and organic phase, can make in the reaction mixture gas, liquid, solid three-state and oil solution and aqueous solution two-phase evenly mixed, simultaneously, methyl alcohol has the surface energy that reduces calcium oxide, wetted surface promotes that slaking reaction can slowly and reposefully carry out.At last, methyl alcohol also can promote the formation of colloidal particle as carrier.
The effect of water in reaction: water is a kind of reaction reagent, slaking reaction needs just to carry out having under the condition of water, and only under the condition that guarantees the water yield, just may make the calcium hydroxide homodisperse of generation, the original place generates the less lime carbonate lattice of particle diameter, and participating in into the glue reaction, the synthetic product viscosity is also less like this.
The effect of secondary accelerator: the introducing of secondary accelerator, can improve the reactive behavior of methyl alcohol, impel the calcium hydroxide homodisperse of generation, the original place generates the less lime carbonate lattice of particle diameter, guarantees that reaction process is steady, and participates in into the glue reaction.
The effect of tensio-active agent: the present invention makes reaction medium that great variety take place owing to having introduced the tensio-active agent alkyl benzene sulphonate (ABS), alkyl benzene sulphonate (ABS) is as a kind of reaction reagent, it can stop the calcium carbonate granule of generation and alkyl sodium salicylate micella to assemble growth, and impel it rapidly to generate load micelle and stably be scattered in the oil solution, simultaneously, alkyl benzene sulphonate (ABS) can generate the mixed micelle that particle diameter is more evenly distributed more for a short time with alkyl salicylate, and participates in into the glue reaction.Investigation result to tensio-active agent is as follows:
Table one, the influence of tensio-active agent to reacting
| Tensio-active agent add-on g | Alkyl salicylate g | TBN mgKOH/g | Ca m% | V
100℃ mm
2/s
|
1
* | 30.0 | 70.0 | 373 | 13.33 | / |
2
* | 20.0 | 80.0 | 365 | 12.56 | / |
3 | 10.0 | 90.0 | 318 | 11.95 | / |
4 | 8.0 | 90.0 | 356 | 13.34 | / |
5 | 6.0 | 90.0 | 358 | 13.28 | / |
6 | 4.5 | 90.0 | 379 | 14.12 | 290.33 |
7 | 3.0 | 90.0 | 377 | 13.76 | / |
8 | 0.0 | 90.0 | 322 | 11.7 | 395.28 |
*Contain 40% base oil
From table one result as can be known, the add-on of tensio-active agent is to the base number important influence of product.
In the experiment thermostability of ultrahigh-basicity composite metal detergent calcium salt, oxidation-resistance, high temperature detergency etc. are evaluated, be the results are shown in Table two, table three.
The assessment of performance result of table two, ultrahigh-basicity composite product
Project | 96-H-144 | Among the 96-H--4 | T-109B | 97-obs-37 | 97-obs-38 |
Tensio-active agent g | / | / | / | 8.0 | 6.0 |
Base number mgKOh/g | 368 | 361 | 278 | 353 | 361 |
The heat pipe oxidation (300 ℃ * 4h) level | 1.0 | 4.0 | 3.5 | 2.0 | 1.5 |
(320 ℃ * 2h) mg of coking amounts | 60.6 | 56.3 | 41.8 | 64.2 | 67.9 |
(165 ℃ * 6h) divide of oxidation stabilities | 20.18 | 13.90 | 28.56 | 21.89 | 31.06 |
SDT % | / | / | 56.2 | 59.7 | 59.3 |
(100 ℃ * 4d) v% of thermostabilitys | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 |
(100 ℃ * 4d) v% of consistencies | +E611 | 0.1 | 0.8 | 0.0 | 0.05 | 0.03 |
+T106 | 1.5 | 0.01 | 0.0 | 0.01 | 0.04 |
Annotate: 96-H-is overbased product (not adding tensio-active agent), and T-109B is the high base number product, and 97-obs-is novel overbased product.
The tribological property evaluation result of table three, ultrahigh-basicity composite product
| P
B N
| P
D N
| ZMZ N | Wear scar diameter (60 * 196) mm |
96-H-144 | 539.0 | 1234.8 | 219.6 | 0.31 |
T-109B | 558.0 | 1568.0 | 226.4 | 0.37 |
Among the 97-H--4 | 558.6 | 1234.8 | 217.6 | 0.36 |
97-obs-37 | 588.0 | 1234.8 | 216.6 | 0.30 |
97-obs-38 | 617.4 | 1568.0 | 269.5 | 0.31 |
The result can find out from table, the consistency of ultrahigh-basicity composite product, and dispersiveness, antiwear and friction reduction property all improves a lot.
The ultrahigh-basicity composite metal detergent calcium salt additive of the inventive method preparation, under identical base number requires, can reduce the add-on of additive in oil product, higher basicity alkyl calcium salicylate (T109B) amount of falling 20m%, because its good high-temperature detergency, oxidation-resistance and thermostability, consistencies etc. can be common in gasoline engine oil and the diesel engine oil, will produce good social benefit and economic benefit.In addition, this agent and the compound use of other additive can guarantee that engine oil has multiple performance, and be significant to improving the lubricating oil acid neutralization capacity.
The following examples are to further specify of the present invention, rather than limit the invention, and spirit of the present invention and protection domain are listed in claims.
Embodiment 1: add 150 milliliters in gasoline, 100 milliliters of methyl alcohol (analytical pure) in having 500 milliliters of there-necked flasks of electric mixer and condensation water trap, alkyl benzene sulphonate (ABS) 3.0 grams, stir, be warming up to 40-50 ℃, drop into 23.0 gram industrial calcium oxide (production of little Pingshan, Lanzhou calcium oxide factory), 9.5 gram water, stir, at this moment visible mixture retrogradation, and be attended by the temperature rise phenomenon, after about 30 minutes, add 90.0 gram alkyl salicylates, stir, control reaction temperature is 45-60 ℃, reacts 1 hour, carries out neutralization reaction.After reaction is finished, add 5.0 gram calcium oxide, 4.0 gram bicarbonate of ammonia, 20 ml methanol again, under 45-60 ℃, carry out the secondary calcify reaction, feed carbonic acid gas after 30 minutes, Ventilation Rate is the 200-250 ml/min, and keeping temperature of reaction is 45-60 ℃, carries out high basicity and reacts about 2 hours.After reaction finishes, be warming up to 110 ℃, steaming engaging benzenemethanol and water add gasoline dilution, cooling, the centrifugal back decompression of removing slag and steam desolventizing and get product.The product calcium contents is 13.62%, and base number is 369mgKOH/g, and kinematic viscosity (100 ℃) is 275.44mm
2/ s.
Embodiment 2: add 150 milliliters in gasoline, 100 milliliters of methyl alcohol (analytical pure) in having 500 milliliters of there-necked flasks of electric mixer and condensation water trap, stir, be warming up to 40-50 ℃, drop into 23.0 gram industrial calcium oxide (production of little Pingshan, Lanzhou calcium oxide factory), 9.5 gram water, stir, at this moment visible mixture retrogradation, and be attended by the temperature rise phenomenon, after about 30 minutes, add 90.0 gram alkyl salicylates, alkyl benzene sulphonate (ABS) 4.5 grams, stir, control reaction temperature is 45-60 ℃, reacts 1 hour, carries out neutralization reaction.After reaction is finished, add 5.0 gram calcium oxide, 4.0 gram bicarbonate of ammonia, 20 ml methanol again, under 45-60 ℃, carry out the secondary calcify reaction, feed carbonic acid gas after 30 minutes, Ventilation Rate is the 200-250 ml/min, and keeping temperature of reaction is 45-60 ℃, carries out high basicity and reacts about 2 hours.After reaction finishes, be warming up to 110 ℃, steaming engaging benzenemethanol and water add gasoline dilution, cooling, the centrifugal back decompression of removing slag and steam desolventizing and get product.The product calcium contents is 14.12%, and base number is 379mgKOH/g, and kinematic viscosity (100 ℃) is 290.33mm
2/ s.
Embodiment 3: add 150 milliliters in gasoline, 60 milliliters of methyl alcohol (analytical pure) in having 500 milliliters of there-necked flasks of electric mixer and condensation water trap, alkyl benzene sulphonate (ABS) 30.0 grams, stir, be warming up to 40-50 ℃, drop into 27.0 gram industrial calcium oxide (production of little Pingshan, Lanzhou calcium oxide factory), 8.8 gram water, stir, at this moment visible mixture retrogradation, and be attended by the temperature rise phenomenon, after about 30 minutes, add 70.0 gram alkyl salicylates, stir, control reaction temperature is 45-60 ℃, reacts 1 hour, carries out neutralization reaction.After reaction is finished, add 5.0 gram calcium oxide, 4.0 gram bicarbonate of ammonia, 20 ml methanol again, under 45-60 ℃, carry out the secondary calcify reaction, feed carbonic acid gas after 30 minutes, Ventilation Rate is the 200-250 ml/min, and keeping temperature of reaction is 45-60 ℃, carries out high basicity and reacts about 2 hours.After reaction finishes, be warming up to 110 ℃, steaming engaging benzenemethanol and water add gasoline dilution, cooling, the centrifugal back decompression of removing slag and steam desolventizing and get product.The product calcium contents is 13.33%, and base number is 373mgKOH/g.
Embodiment 4: add 150 milliliters in gasoline, 80 milliliters of methyl alcohol (analytical pure) in having 500 milliliters of there-necked flasks of electric mixer and condensation water trap, alkyl benzene sulphonate (ABS) 20.0 grams, stir, be warming up to 40-50 ℃, drop into 27.0 gram industrial calcium oxide (production of little Pingshan, Lanzhou calcium oxide factory), 10.2 gram water, stir, at this moment visible mixture retrogradation, and be attended by the temperature rise phenomenon, after about 30 minutes, add 80.0 gram alkyl salicylates, stir, control reaction temperature is 45-60 ℃, reacts 1 hour, carries out neutralization reaction.After reaction is finished, add 5.0 gram calcium oxide, 4.0 gram bicarbonate of ammonia, 20 ml methanol again, under 45-60 ℃, carry out the secondary calcify reaction, feed carbonic acid gas after 30 minutes, Ventilation Rate is the 200-250 ml/min, and keeping temperature of reaction is 45-60 ℃, carries out high basicity and reacts about 2 hours.After reaction finishes, be warming up to 110 ℃, steaming engaging benzenemethanol and water add gasoline dilution, cooling, the centrifugal back decompression of removing slag and steam desolventizing and get product.The product calcium contents is 13.91%, and base number is 374mgKOH/g.