CN1334325A - Process for preparing ultrahigh-basicity composite metal detergent - Google Patents
Process for preparing ultrahigh-basicity composite metal detergent Download PDFInfo
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- CN1334325A CN1334325A CN 00122002 CN00122002A CN1334325A CN 1334325 A CN1334325 A CN 1334325A CN 00122002 CN00122002 CN 00122002 CN 00122002 A CN00122002 A CN 00122002A CN 1334325 A CN1334325 A CN 1334325A
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- methyl alcohol
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- 239000003599 detergent Substances 0.000 title claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 16
- 239000002184 metal Substances 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 84
- -1 ammonia compound Chemical class 0.000 claims abstract description 26
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000292 calcium oxide Substances 0.000 claims abstract description 22
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 8
- 230000002308 calcification Effects 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000013543 active substance Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 17
- 239000003921 oil Substances 0.000 claims description 15
- 238000010792 warming Methods 0.000 claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 229960001860 salicylate Drugs 0.000 claims description 8
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 159000000007 calcium salts Chemical class 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 235000011089 carbon dioxide Nutrition 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000001465 metallisation Methods 0.000 claims description 4
- 239000010705 motor oil Substances 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 150000001555 benzenes Chemical class 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 208000004434 Calcinosis Diseases 0.000 claims 1
- 229940095054 ammoniac Drugs 0.000 claims 1
- 235000011837 pasties Nutrition 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 9
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 5
- 229960004217 benzyl alcohol Drugs 0.000 description 5
- 230000006837 decompression Effects 0.000 description 5
- 238000010025 steaming Methods 0.000 description 5
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010687 lubricating oil Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 238000009423 ventilation Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000000693 micelle Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229960004025 sodium salicylate Drugs 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000010710 diesel engine oil Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010711 gasoline engine oil Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- YXJYBPXSEKMEEJ-UHFFFAOYSA-N phosphoric acid;sulfuric acid Chemical compound OP(O)(O)=O.OS(O)(=O)=O YXJYBPXSEKMEEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Abstract
A composite detergent with ultra-high basicity for metals is prepared from alkylsalicylic acid, calcium oxide, and promoter (methanol and ammonia compound), through proportional mixing and two-step calcification. Its advantages are high basicity (350mgKOH/g), high high-temp detergency, low-temp dispersity, and anticorrosion and antiwear performance, and better compatibility with sulfonate-type detergent.
Description
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
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.
| 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 | |
The tribological property evaluation result of table three, ultrahigh-basicity composite product
| ????PB ????N | ????PD ????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-3?7 | ????588.0 | ????1234.8 | ????216.6 | ????0.30 |
| ?97-obs-3?8 | ????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.
Claims (5)
1, a kind of preparation method of ultrahigh-basicity composite metal detergent calcium salt product, it is characterized in that: introduce specific surfactant in this method and carry out two single metal metallization processes, promptly in there-necked flask, drop into the gasoline and the methyl alcohol of metering, stirring is warming up to 30-60 ℃, drop into the industrial calcium oxide of metering, the water that adds metering simultaneously, observe mixture retrogradation gradually in the flask, become pasty state by bulk, and be attended by the temperature rise phenomenon, after stirring about 30 minutes, add the alkyl salicylate of metering and specific tensio-active agent, stirring reaction, keep temperature of reaction 40-60 ℃, carry out neutralization reaction 1 hour, and added metered calcium oxide thereafter, methyl alcohol and Ammonia secondary accelerator are kept reaction 30 minutes under 40-60 ℃, feed a certain amount of carbon dioxide then, carry out high basicity reaction 2 hours, after reaction finished, separating treatment got product.Promotor is used methyl alcohol, secondary accelerator uses ammonia and ammonium salt, the ratio of components of each component has certain ratio, in 90 parts of (weight) alkyl salicylates, 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, temperature of reaction is controlled between 40-60 ℃, and specific surfactant should be two alkyl or monoalkylated benzenes sulfonic acid, and its molecular-weight average is 400-500.
2, method according to claim 1 is characterized in that: secondary accelerator can be ammoniac compounds such as ammoniacal liquor, volatile salt, bicarbonate of ammonia.
3, method according to claim 1 is characterized in that: calcium oxide and methyl alcohol must add in two steps, promptly adopt secondary calcification mode, and will introduce a kind of tensio-active agent and secondary accelerator.
4, method according to claim 1 is characterized in that: tensio-active agent and alkyl salicylate add simultaneously, or add simultaneously with methyl alcohol, gasoline.
5, method according to claim 1 is characterized in that: its base number of the product of preparation is greater than 350mgKOH/g, and calcium contents is not more than 400mm greater than 12.5,100 ℃ of kinematic viscosity
2/ s is applicable to various other I. C. engine oils of level and bunker oil, railroad engines oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00122002 CN1126807C (en) | 2000-07-19 | 2000-07-19 | Process for preparing ultrahigh-basicity composite metal detergent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00122002 CN1126807C (en) | 2000-07-19 | 2000-07-19 | Process for preparing ultrahigh-basicity composite metal detergent |
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| Publication Number | Publication Date |
|---|---|
| CN1334325A true CN1334325A (en) | 2002-02-06 |
| CN1126807C CN1126807C (en) | 2003-11-05 |
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| CN 00122002 Expired - Fee Related CN1126807C (en) | 2000-07-19 | 2000-07-19 | Process for preparing ultrahigh-basicity composite metal detergent |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102015983A (en) * | 2008-09-05 | 2011-04-13 | Omg美国公司 | Overbased metal carboxylate complex grease and process for making |
| CN102295971A (en) * | 2011-07-25 | 2011-12-28 | 金桐石油化工有限公司 | High base number calcium heavy alkyl benzene sulfonate detergent and preparation method thereof |
| CN1896203B (en) * | 2005-07-14 | 2013-02-20 | 英菲诺姆国际有限公司 | Method of improving the compatibility of an overbased detergent with other additives in a lubricating oil composition |
| CN106187827A (en) * | 2016-07-13 | 2016-12-07 | 新乡市瑞丰新材料股份有限公司 | A kind of preparation method of sulfonate |
| CN110194983A (en) * | 2019-04-23 | 2019-09-03 | 青岛博士德润滑科技有限公司 | A kind of nano boric acid lanthanum detersive and its preparation method and application |
-
2000
- 2000-07-19 CN CN 00122002 patent/CN1126807C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1896203B (en) * | 2005-07-14 | 2013-02-20 | 英菲诺姆国际有限公司 | Method of improving the compatibility of an overbased detergent with other additives in a lubricating oil composition |
| CN102015983A (en) * | 2008-09-05 | 2011-04-13 | Omg美国公司 | Overbased metal carboxylate complex grease and process for making |
| CN102295971A (en) * | 2011-07-25 | 2011-12-28 | 金桐石油化工有限公司 | High base number calcium heavy alkyl benzene sulfonate detergent and preparation method thereof |
| CN106187827A (en) * | 2016-07-13 | 2016-12-07 | 新乡市瑞丰新材料股份有限公司 | A kind of preparation method of sulfonate |
| CN106187827B (en) * | 2016-07-13 | 2018-09-21 | 新乡市瑞丰新材料股份有限公司 | A kind of preparation method of sulfonate |
| CN110194983A (en) * | 2019-04-23 | 2019-09-03 | 青岛博士德润滑科技有限公司 | A kind of nano boric acid lanthanum detersive and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1126807C (en) | 2003-11-05 |
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