CN1209429A - Process for preparing super-high basicity-value calcium alkyl salicylate - Google Patents
Process for preparing super-high basicity-value calcium alkyl salicylate Download PDFInfo
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- CN1209429A CN1209429A CN 97116375 CN97116375A CN1209429A CN 1209429 A CN1209429 A CN 1209429A CN 97116375 CN97116375 CN 97116375 CN 97116375 A CN97116375 A CN 97116375A CN 1209429 A CN1209429 A CN 1209429A
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Abstract
The invented preparation method uses alkyl salicylic acid and calcium oxide as raw material, and uses methyl alcohol and ammonia type compound as accelerator to synthesize the calcium alkyl salicylate with extra high base number. Said invented synthesis process is applicable to industrial calcium oxide with different activity, and the invented synthetic product possesses a certain antioxidative and corrosion-resisting property as well as high-temp. cleaning property, so that it is an excellent additive for lubricating agent.
Description
The invention relates to a preparation method of calcium alkyl salicylate with an ultrahigh base number, belonging to the field of lubricating oil.
As is well known, the lubricating oil detergent alkyl salicylate has been the main additive used in various internal combustion engine oils, and among them, the low, medium and high base number calcium salt products have been widely used. The agent has better high-temperature detergency, oxidation resistance and corrosion resistance. In recent years, with the development of engine design toward miniaturization, high power and high speed to improve fuel economy and work efficiency, a lubricant detergent with good thermal stability, high base number, low viscosity and low turbidity is required, and therefore, ultra-high base number products are increasingly favored. The patent is more about the production and preparation of the sulfonate with the ultrahigh base number, but the patent technology about the alkyl water field acid salt with the ultrahigh base number is not reported.
The invention aims to provide a preparation method of calcium alkyl salicylate with an ultrahigh base number, so that an additive with excellent performance can be provided for lubricating oil.
The preparation method of the ultrahigh-base-number calcium alkyl water field comprises the following steps: installing a three-neck flask with an electric stirring and condensing dehydrator, adding metered gasoline (industrial products) and methanol (industrial products), starting a stirrer, heating to 40-50 ℃, adding metered industrial calcium oxide (with the purity of more than 93%), adding metered water, observing that a mixture in the flask gradually thickens and becomes pasty from a block shape along with the temperature rise phenomenon, stirring for about 30 minutes, adding metered alkyl salicylic acid, stirring for reaction, maintaining the reaction temperature at 45-60 ℃, performing a neutralization reaction for about 1 hour, adding metered calcium oxide, methanol and ammonia promoters, maintaining the reaction for 30 minutes at 45-60 ℃, then introducing a certain amount of carbon dioxide gas, performing a high-alkalinity reaction for about 2 hours, heating to 110 ℃ after the reaction is finished, evaporating methanol and water, adding gasoline for dilution, cooling, centrifuging, and finally decompressing and evaporating to remove the solvent to obtain the product.
A preparation method of calcium alkyl water field with ultrahigh base number is characterized in that: adding metered solvent and methanol into a reactor, stirring, heating to 40-50 ℃, adding metered industrial calcium oxide, adding metered water, continuously stirring, keeping the reaction for about 30 minutes, then adding metered alkyl salicylic acid, keeping the reaction temperature to 45-60 ℃, carrying out neutralization reaction for 1 hour, and then supplementing metered calcium oxide, methanol and a promoter. After the reaction is continued for half an hour, a certain amount of carbon dioxide is introduced to carry out high alkalinity reaction for about 2 hours, after the reaction is finished, the temperature is raised to 110 ℃, methanol and water are evaporated and removed, then a solvent is added for dilution, the mixture is cooled and centrifuged, finally the solvent is evaporated and removed to obtain a product, the promoter uses the methanol, the promoter uses the ammonia and ammonium salt, the mixture ratio of the components is a certain proportion, based on 90 parts by weight of alkyl salicylic acid (about 40 percent of oil), the calcium oxide is 27 to 30 parts, the methanol is 50 to 120 parts, the water is 9.5 to 12.0 parts, the ammonia promoter is 1.5 to 6.5 parts, the solvent is 40 to 140 parts, the carbon dioxide is 44 to 100 parts, the reaction temperature is controlled between 45 and 60 ℃, preferably within 50 to 55 DEG CThe reaction steps are divided into three steps: curing reaction, neutralization reaction and high alkalinity reaction. The reaction system can be suitable for calcium oxide of different grades, and can be reagent grade, industrial grade one or industrial grade two, the solvent for reaction can be straight-run gasoline with the distillation range of 60-160 ℃, and the alkyl salicylic acid as the reaction raw material has the structure as follows:
wherein R is C8-20Alkyl chain of (2).
The methanol must be a chemical agent or industrial product with purity greater than 95%, and the auxiliary promoter may be ammonia, ammonium carbonate or ammonium bicarbonate, preferably chemically pure ammonium bicarbonate. Methanol, water and an auxiliary accelerator are main factors influencing the base number and viscosity of the product. The amount of methanol is suitably 70-95 g/90 g of alkyl salicylic acid, and the amount of water is suitably 10.0-11.7 g/90.0 g of alkyl salicylic acid. The synthesized product has excellent oxidation resistance, thermal stability, cleaning and dispersing performance.
The synthesis reaction process of the ultrahigh-base-number calcium alkyl salicylate comprises the following steps:
curing reaction: (vii) neutralization reaction (1):
high alkalinity reaction: 〖3〗
the function of methanol:
the methanol is used as carrier of inorganic phase and organic phase, so that the three phases of gas, liquid and solid and the two phases of oil solution and water solution can be uniformly mixed in the reaction mixture, and at the same time, the methanol can reduce the surface energy of calcium oxide, moisten the surface, promote the curing reaction to slowly and smoothly proceed, and finally, the methanol is used as carrier, and can also promote the formation of colloidal particles.
Role of water in the reaction:
water is a reaction reagent, the curing reaction can be carried out under the condition of water, and the generated calcium hydroxide can be uniformly dispersed only under the condition of ensuring the water quantity, so that calcium carbonate crystal lattices with smaller grain sizes are generated in situ and participate in the gelling reaction (4), and the viscosity of the synthesized product is also lower.
The influence of different aeration rates and time on the base number and the viscosity of the synthesized product is also investigated in the test, and the influence of the aeration rate and the aeration time of the carbon dioxide on the base number and the viscosity of the product is found to be small.
The thermal stability, oxidation resistance and detergency of the ultrahigh-base-number alkyl calcium salicylate salt are evaluated in the experiment, and the results are shown in tables 1 and 2:
TABLE 1 Performance evaluation results for ultra-high base number products
As can be seen from the evaluation results in Table 1, NH was added in the same amount4HCO3As an auxiliary accelerator, the obtained product has lower coke formation amount and oxidation score, which shows that the salt has better detergency and oxidation resistance.
TABLE 2 use of ultra high base number products in marine oils
| The addition amount of the main agent | TBN mgKOH/g | V100℃ mm/s | Corrosion of copper sheet Stage | Pour point ℃ | Amount of thermal precipitation mg | Flash point ℃ | PB N | PD N | ZMZ N | V40℃ | |
| CY-2 | T109B 10.0m％ | 76.6 | 19.63 | 1a | -2 | 0 | 213 | 931 | 2450 | 445.9 | 266.0 |
| CY-4 | Ultra-base number product 7.9m％ | 76.93 | 20.59 | 1a | -3 | 0 | 213 | 980 | 2450 | 454.7 | 285.8 |
As can be seen from the results in Table 2, the TBN70 marine oil prepared by respectively using T109B and the ultrahigh-base-number calcium alkyl salicylate as the main agents has the advantages that the addition amount of the main agent is reduced by 2.1 m% under the condition of similar basic performances, the cost is greatly saved, and the oil change period is delayed.
The ultrahigh-base-number calcium alkyl salicylate additive prepared by the method can reduce the addition amount of the additive in oil products under the same base number requirement, and the reduction amount of the higher-base-number calcium alkyl salicylate (T109B) is 20m percent. In addition, the lubricating oil additive is compounded with other additives for use, so that the lubricating oil has various performances, and has important significance for improving the neutralizing capacity of lubricating oil acid.
The following examples are further illustrative of the present invention, but are not intended to be limiting thereof, the spirit and scope of the invention being set forth in the appended claims.
Example 1: 100ml of gasoline and 80ml of methanol (analytically pure) are added into a 500ml three-mouth bottle with an electric stirrer and a condensation dehydrator, the mixture is stirred and heated to 40-50 ℃, 23.0g of industrial calcium oxide (produced by calcium oxide factory in Xiao-Pongshan of Lanzhou) and 10.3g of water are added, the mixture is stirred, the mixture becomes thick along with the temperature rise phenomenon at this time, 90.0g of alkyl salicylic acid (with the acid value of 73.4mgKOH/g and the oil content of 40%) is added after about 30min, the mixture is stirred, the reaction temperature is controlled to be 50-55 ℃, the reaction is carried out for 1h, the neutralization reaction is carried out, after the reaction is finished, 5.0g of calcium oxide, 6.5g of ammonium bicarbonate and 10ml of methanol are added, the secondary calcification reaction is carried out at the temperature of 50-55 ℃, carbon dioxide is introduced after 30min, the aeration rate is 250ml/min, the reaction temperature is kept to be 50-55. After the reaction is finished, the temperature is raised to 110 ℃, methanol and water are evaporated, 150g of gasoline is added for dilution, and the mixture is cooled. Centrifuging the reaction product at the rotating speed of 4000r/min for about 30min, removing residues, and evaporating to remove the solvent to obtain the product. The calcium content of the product is 12.44 percent, the base number is 354mgKOH/g, and the kinematic viscosity (100 ℃) is 91.01 mm/s.
Example 2: the operation of example 1 was followed, and different feeding modes and feeding amounts of calcium oxide were examined, and the results are shown in Table 3.
Table 3, investigation results of calcium oxide feeding mode and feeding amount
As can be seen from the results in Table 3, the secondary calcification method has good reaction repeatability and enhanced adaptability to the accelerator. And after the dosage of the calcium oxide is increased, the base number of the product is obviously increased. The secondary calcification mode is stable and reliable, and the process route established on the basis of the secondary calcification mode is superior to the primary calcification process.
Example 3: the procedure of example 1 was followed, different promoters were selected, the base number of the synthesized product was up to 350mgKOH/g, and the calcium content was close to or up to 12.5 m%, and the experimental results are shown in Table 4.
TABLE 4 Effect of different boosters on product Properties
As can be seen from Table 4, the base number and calcium content of the product do not change significantly with the change of the co-accelerator, but the viscosity difference is large, so the co-accelerator can be selected according to different viscosity requirements.
Example 4: the procedure of example 1 is followed for the preparation of methanol, water and auxiliary NH4HCO3Amount of CO2The aeration time and the like were examined, and the test results are shown in Table 5.
TABLE 5 influence of different reaction conditions on the product Properties
As can be seen from the table, methanol, water amount, NH4HCO3The dosage of the product has obvious influence on the base number and the viscosity of the product, and the aeration time has little influence on the base number and the viscosity of the product.
Claims (6)
1. A process for preparing the ultrahigh-basicity alkyl salicylate includes such steps as adding solvent and methanol to reactor, stirring while heating to 40-60 deg.C, adding industrial calcium oxide and water, stirring for 30min, adding alkyl salicylate, neutralizing reaction at 45-60 deg.C for 1 hr, adding calcium oxide, methanol and ammonia promoter, reacting at 45-60 deg.C for 30min, introducing carbon dioxide, high-basicity reaction for 2 hr, heating to 110 deg.C, evaporating methanol and water, diluting with solvent, cooling, centrifugal separation, evaporating solvent to obtain methanol and ammonia compound, and mixing the components in a certain proportion, based on 90 parts by weight of alkyl salicylic acid (40% of oil), 27-30 parts of calcium oxide, 50-120 parts of methanol, 9.5-12.0 parts of water, 1.6-6.5 parts of auxiliary accelerator, 40-140 parts of solvent and 44-100 parts of carbon dioxide.
2. The method of claim 1, wherein: the reaction system can be suitable for different grades of industrial calcium oxide.
3. The method of claim 1, wherein: the solvent for reaction may be straight-run gasoline with distillation range of 60-180 deg.C, or may be material with boiling point higher than 120 deg.C, such as xylene.
4. The method of claim 1, wherein: the structure of the reaction raw material alkyl salicylic acid is as follows:
wherein R is C8-20Alkyl chain of (2).
5. The method of claim 1, wherein: the methanol is necessary to be a chemical reagent or industrial product with the purity of more than 95 percent, and the auxiliary promoter can be ammonia water, ammonium carbonate or ammonium bicarbonate, and is preferably chemically pure or industrial ammonium bicarbonate.
6. The method of claim 1, wherein: the calcium oxide and methanol must be added in two steps, i.e. by means of secondary calcification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN97116375A CN1064039C (en) | 1997-08-22 | 1997-08-22 | Process for preparing super-high basicity-value calcium alkyl salicylate |
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| CN97116375A CN1064039C (en) | 1997-08-22 | 1997-08-22 | Process for preparing super-high basicity-value calcium alkyl salicylate |
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| CN1209429A true CN1209429A (en) | 1999-03-03 |
| CN1064039C CN1064039C (en) | 2001-04-04 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104371553A (en) * | 2013-08-14 | 2015-02-25 | 安集微电子（上海）有限公司 | Chemical mechanical polishing liquid and applications thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1144216A (en) * | 1995-09-01 | 1997-03-05 | 中国石化兰州炼油化工总厂 | Method for preparation of calcium alkyl salicylate with high base number |
| CN1042742C (en) * | 1995-11-02 | 1999-03-31 | 中国石化兰州炼油化工总厂 | Process for preparing lubricating oil additive |
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- 1997-08-22 CN CN97116375A patent/CN1064039C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104371553A (en) * | 2013-08-14 | 2015-02-25 | 安集微电子（上海）有限公司 | Chemical mechanical polishing liquid and applications thereof |
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