CN113528215B - Preparation method of high-DBN calcium sulfonate for lubricating grease - Google Patents
Preparation method of high-DBN calcium sulfonate for lubricating grease Download PDFInfo
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- CN113528215B CN113528215B CN202110777408.XA CN202110777408A CN113528215B CN 113528215 B CN113528215 B CN 113528215B CN 202110777408 A CN202110777408 A CN 202110777408A CN 113528215 B CN113528215 B CN 113528215B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M121/00—Lubricating compositions characterised by the thickener being a compound of unknown or incompletely defined constitution
- C10M121/04—Reaction products
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M123/00—Lubricating compositions characterised by the thickener being a mixture of two or more compounds covered by more than one of the main groups C10M113/00 - C10M121/00, each of these compounds being essential
- C10M123/06—Lubricating compositions characterised by the thickener being a mixture of two or more compounds covered by more than one of the main groups C10M113/00 - C10M121/00, each of these compounds being essential at least one of them being a compound of the type covered by group C10M121/00
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/02—Mixtures of base-materials and thickeners
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/26—Overbased carboxylic acid salts
- C10M2207/2613—Overbased carboxylic acid salts used as thickening agents
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/52—Base number [TBN]
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
The invention discloses a preparation method of high-DBN calcium sulfonate for lubricating grease, belonging to the technical field of calcium sulfonate, comprising the steps of adding a solvent, base oil, alcohol, calcium oxide, water and a carboxylic acid compound into a reaction container; dropwise adding sulfonic acid into the reaction container, and heating to 80-85 ℃ for neutralization reaction; adding calcium oxide and water into a reaction container, and heating to 80-85 ℃ to perform primary carbonization reaction; heating to remove alcohol, water and solvent, and cooling to 50-55 deg.C; adding alcohol, calcium oxide, water and a solvent into a reaction container, cooling to 45-50 ℃, and then carrying out secondary carbonization reaction; removing alcohol and water, settling, separating, centrifuging the upper layer reaction liquid, and distilling under reduced pressure to obtain the calcium alkyl benzene sulfonate product. The synthesis of high-finished product DBN calcium sulfonate is realized by adjusting process parameters and the types of additives, wherein the DBN is about 60; the preparation method has the advantages of wide source of production raw materials, simple operation of production process, continuous production and low production cost.
Description
Technical Field
The invention relates to the technical field of calcium sulfonate, in particular to a preparation method of high-DBN calcium sulfonate for lubricating grease.
Background
The composite calcium sulfonate-based lubricating grease is an important lubricating grease and is generated by converting and compounding high-base-number calcium sulfonate. The existing common high-base-number calcium sulfonate is mainly TBN400 calcium sulfonate, and the sulfur content of the existing sulfonate for the lubricating grease is higher, so that the production cost of the sulfonate is high, and the prepared lubricating grease is softer; the existing sulfonate TBN for the lubricating grease is about 435, so that the ash content of the prepared lubricating grease is high; the DBN finished product is low, and more transforming agents, functional agents and filling oil cannot be added during the preparation of the lubricating grease, so that the production cost of the lubricating grease is high. Therefore, it is very meaningful to develop a calcium sulfonate synthesis process with high base number, high finished product DBN and low sulfur content.
The lubricating grease prepared by the existing high-base-number calcium sulfonate has the defects of high ash content, low dropping point, high cone penetration, poor stability and the like, so that the lubricating grease is frequently replaced in the using process, and heavy economic burden is brought to lubricating grease users.
Disclosure of Invention
Aiming at the defects existing in the problems, the invention provides a preparation method of calcium sulfonate with high DBN for lubricating grease.
In order to achieve the above object, the present invention provides a preparation method of calcium high DBN sulfonate for grease, comprising:
adding 250-350 parts of solvent, 150-200 parts of base oil, 30-70 parts of alcohol, 20-30 parts of calcium oxide, 3-10 parts of water and 30-60 parts of carboxylic acid compound into a reaction vessel according to parts by weight, heating to 55-60 ℃, and uniformly stirring;
82-155 parts of sulfonic acid is dripped into the reaction vessel, and after dripping is finished, 30-40 parts of polyisobutylene succinic anhydride is dripped, and the temperature is raised to 80-85 ℃ for neutralization reaction;
after the neutralization reaction is finished, adding 40-50 parts of calcium oxide and 10-20 parts of water into the reaction container, heating to 80-85 ℃, and continuously introducing carbon dioxide into the reaction container to perform carbonization reaction;
after the primary carbonization reaction is finished, keeping the temperature unchanged, continuously adding 40-50 parts of calcium oxide and 10-20 parts of water into the reaction container, and continuously introducing carbon dioxide into the reaction container to perform a secondary carbonization reaction;
after the secondary carbonization reaction is finished, heating to remove alcohol, water and solvent, and cooling to 50-55 ℃;
adding 40-80 parts of alcohol, 40-50 parts of calcium oxide, 10-20 parts of water and 250-350 parts of solvent into the reaction container, cooling to 45-50 ℃, and continuously introducing carbon dioxide into the reaction container to perform carbonization reaction for three times;
after the third carbonization reaction is finished, removing alcohol and water, settling and separating, and centrifuging and distilling the upper layer reaction solution under reduced pressure to obtain the calcium sulfonate product.
Preferably, the mass ratio of calcium oxide to carbon dioxide in the primary carbonization reaction and the secondary carbonization reaction is 1:0.45-1:0.55;
the mass ratio of calcium oxide to carbon dioxide in the third carbonization reaction is 1:0.85-1:0.95.
preferably, the alcohol is one or more of C1-C8 alcohol;
the base oil is one or more of 100N, 100SN, 150N, 150SN, 500N, 500SN and 150 BS;
the carboxylic acid compound is one or more of mono-carboxylic acid and dicarboxylic acid;
the solvent is one or more of benzene, toluene, xylene, 120# solvent, 200# solvent, petroleum ether, n-hexane and n-heptane.
Preferably, the sulfonic acid comprises alkylbenzene sulfonic acid and petroleum sulfonic acid, and the mass ratio of the alkylbenzene sulfonic acid to the petroleum sulfonic acid is 7:3.
preferably, the carbon chain of the alkylbenzene sulfonic acid has 12 to 30 carbon atoms.
Preferably, the carbon chain of the alkylbenzene sulfonic acid has 18 to 24 carbon atoms.
Preferably, the carbon chain of the alkylbenzene sulfonic acid has C22 to C24 carbon atoms.
Preferably, 250-350 parts of solvent, 150-200 parts of base oil, 30-70 parts of alcohol, 20-30 parts of calcium oxide, 3-10 parts of water and 30-60 parts of carboxylic acid compound are added into a reaction vessel according to the parts by weight, and after the temperature is raised to 55-60 ℃, the mixture is uniformly stirred, and the method comprises the following steps:
under the condition of protecting gas, adding 250-350 parts of solvent, 150-200 parts of base oil and 30-70 parts of alcohol into the reaction vessel, and stirring for 20min;
after uniformly stirring, adding 20-30 parts of calcium oxide and 3-10 parts of water into the reaction container, and stirring for 30min;
then, 30 to 60 parts of a carboxylic acid compound is added dropwise to the reaction vessel.
Preferably, the step of dropwise adding 82-155 parts of sulfonic acid into the reaction container, and after the dropwise adding is finished, heating to 80-85 ℃ to perform neutralization reaction comprises the following steps:
dropwise adding 82-155 parts of sulfonic acid into the reaction container at a constant speed for 60-90min;
and after the dropwise addition is finished, dropwise adding 30-40 parts of polyisobutylene succinic anhydride, heating to 80-85 ℃ for neutralization reaction, and measuring the pH value of the reaction solution by using a pH meter after the reaction is carried out for 1.5h so as to control the pH value to be more than 10.
Compared with the prior art, the invention has the beneficial effects that:
the synthesis of high-finished product DBN calcium sulfonate is realized by adjusting process parameters and the types of additives, wherein the DBN is about 60; the preparation method has the advantages of wide source of production raw materials, simple operation of production process, continuous production and low production cost.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention is described in further detail below:
the invention provides a preparation method of high-DBN calcium sulfonate for lubricating grease, which comprises the following steps:
adding 250-350 parts of solvent, 150-200 parts of base oil, 30-70 parts of alcohol, 20-30 parts of calcium oxide, 3-10 parts of water and 30-60 parts of carboxylic acid compound into a reaction vessel according to parts by weight, heating to 55-60 ℃, and uniformly stirring;
specifically, under the condition of protective gas, adding 250-350 parts of solvent, 150-200 parts of base oil and 30-70 parts of alcohol into the reaction vessel, and stirring for 20min;
after uniformly stirring, adding 20-30 parts of calcium oxide and 3-10 parts of water into the reaction container, and stirring for 30min;
then, 30 to 60 parts of a carboxylic acid compound is added dropwise to the reaction vessel.
Dropwise adding sulfonic acid into the reaction container, after dropwise adding, dropwise adding 30-40 parts of polyisobutylene succinic anhydride, and heating to 80-85 ℃ for neutralization reaction;
specifically, 82-155 parts of sulfonic acid is dropwise added into the reaction container at a constant speed for 60-90min;
and after the dropwise addition is finished, dropwise adding 30-40 parts of polyisobutylene succinic anhydride, heating to 80-85 ℃ for neutralization reaction, and measuring the pH value of the reaction solution by using a pH meter after the reaction is carried out for 1.5h so as to control the pH value to be more than 10.
Further, the sulfonic acid comprises alkylbenzene sulfonic acid and petroleum sulfonic acid, and the mass ratio of the alkylbenzene sulfonic acid to the petroleum sulfonic acid is 7:3. the carbon number of the carbon chain of the alkylbenzene sulfonic acid is C12-C30; more preferably C18 to C24; still more preferably, the number of carbon atoms is from C22 to C24.
After the neutralization reaction is finished, adding calcium oxide and water into the reaction vessel, and heating to 80-85 ℃ to perform primary carbonization reaction;
adding 40-50 parts of calcium oxide and 10-20 parts of water into a reaction container, heating to 80-85 ℃, and continuously introducing carbon dioxide into the reaction container to perform carbonization reaction; wherein the mass ratio of calcium oxide to carbon dioxide is 1:0.45-1:0.55;
after the primary carbonization reaction is finished, keeping the temperature unchanged, continuously adding 40-50 parts of calcium oxide and 10-20 parts of water into the reaction container, and continuously introducing carbon dioxide into the reaction container to perform a secondary carbonization reaction; wherein the mass ratio of calcium oxide to carbon dioxide is 1:0.45-1:0.55;
after the secondary carbonization reaction is finished, heating to remove alcohol, water and solvent, and cooling to 50-55 ℃;
adding 40-80 parts of alcohol, 40-50 parts of calcium oxide, 10-20 parts of water and 250-350 parts of solvent into a reaction container, cooling to 45-50 ℃, and continuously introducing carbon dioxide into the reaction container to perform carbonization reaction for three times; wherein the mass ratio of calcium oxide to carbon dioxide is 1:0.85-1:0.95.
after the third carbonization reaction is finished, removing alcohol and water, settling and separating, and centrifuging and distilling the upper layer reaction liquid under reduced pressure to obtain the calcium alkyl benzene sulfonate product.
Furthermore, after the lower layer solid is extracted by a solvent, a certain amount of calcium alkyl benzene sulfonate product can be obtained.
In the embodiment, the alcohol is one or more of C1-C8 alcohol; for example: methanol, acetic acid, propanol, butanol, ethylene glycol, octanol and the like;
the base oil is one or more of 100N, 100SN, 150N, 150SN, 500N, 500SN and 150 BS;
the carboxylic acid compound is one or more of mono-carboxylic acid and dicarboxylic acid; for example: formic acid, acetic acid, malonic acid, decanoic acid, sebacic acid, dodecahydroxystearic acid, oleic acid, stearic acid, dodecenylsuccinic acid, succinic acid, polyisobutylene succinic anhydride, and the like;
the solvent is one or more of benzene, toluene, xylene, 120# solvent, 200# solvent, petroleum ether, n-hexane and n-heptane.
Example 1
Putting 300Kg of solvent, 180Kg of base oil and 50Kg of alcohol into a 1000L reaction vessel, and stirring for 20min to mix uniformly; then adding 20Kg of calcium oxide and 5Kg of water, and stirring for 30min; dripping 5Kg of formic acid and 5Kg of acetic acid within 30min, then dripping 60Kg of monoalkyl benzene sulfonic acid, 45Kg of dialkyl benzene sulfonic acid, 45Kg of petroleum sulfonic acid and sulfonic acid in turn within 75-90min at constant speed, and then dripping 30Kg of polyisobutylene succinic anhydride, wherein the temperature is raised to 80-85 ℃; and (5) neutralizing for 1.5h, and recording the pH value of a neutralization reaction solution. Then adding 40Kg of calcium oxide and 10Kg of water, carrying out carbonization reaction at 80-85 ℃, introducing carbon dioxide at a gas speed of 350g/min, introducing gas to 21Kg, adding 30mgKOH/g of primary reaction solution free alkali, adding 40Kg of calcium oxide and 10Kg of water again while maintaining the temperature, and then adding the calcium oxide and the water again while maintaining the temperatureVentilating to 50Kg; namely 21Kg of first aeration and 29Kg of second aeration, wherein the second free alkali is 32mgKOH/g; then heating to remove alcohol, water and solvent, and cooling the material to 50-55 ℃; adding 300Kg of solvent, 80Kg of alcohol, 45Kg of calcium oxide and 12Kg of water again, introducing carbon dioxide at 45-50 ℃ at a gas flow rate of 200g/min, and introducing gas to 84Kg, wherein the free alkali at three times is 14mgKOH/g. And after the carbonization is finished, dealcoholizing water to 120 ℃, then precipitating and filtering, and then carrying out reduced pressure distillation on the filtrate to remove the solvent. The base number of the product is 407mgKOH/g, and the kinematic viscosity at 100 ℃ is 83mm 2 And/s, the DBN of the finished product is 42mgKOH/g, and the precipitation value is 0.07.
Example 2
Putting 300Kg of solvent, 180Kg of base oil and 50Kg of alcohol into a 1000L reaction kettle, and stirring for 20min to mix uniformly; then 20Kg of calcium oxide and 5Kg of water are added and stirred for 30min. Dripping 5Kg of formic acid and 5Kg of acetic acid within 30min, then dripping 60Kg of monoalkyl benzene sulfonic acid, 45Kg of dialkyl benzene sulfonic acid and 45Kg of petroleum sulfonic acid in turn, finishing dripping the sulfonic acid at a constant speed within 75-90min, and then dripping 30Kg of polyisobutylene succinic anhydride, and heating to 80-85 ℃; and (5) neutralizing for 1.5h, and recording the pH value of a neutralization reaction solution. Then adding 40Kg of calcium oxide and 10Kg of water, carrying out carbonization reaction at 80-85 ℃, introducing carbon dioxide at the air speed of 350g/min, introducing air to 21Kg, adding 40Kg of calcium oxide and 10Kg of water again while keeping the temperature unchanged, and then introducing air to 42Kg, wherein the concentration of the secondary free alkali is 45mgKOH/g; then heating to remove alcohol, water and solvent, and cooling the material to 50-55 ℃. Adding 300Kg of solvent, 80Kg of alcohol, 45Kg of calcium oxide, and 12Kg of water again, introducing carbon dioxide at a gas speed of 200g/min at 45-50 deg.C to 84Kg, and introducing the third time free alkali to 19mgKOH/g. And after the carbonization is finished, dealcoholizing water to 120 ℃, then precipitating and filtering, and then carrying out reduced pressure distillation on the filtrate to remove the solvent. The product has base number of 418mgKOH/g and kinematic viscosity of 86mm at 100 DEG C 2 (s), DBN of the finished product was 60mgKOH/g, and the precipitation number was 0.06.
Example 3
300Kg of solvent, 180Kg of base oil and 50Kg of alcohol are put into a 1000L reaction kettle and stirred for 20min to be uniformly mixed. Then 20Kg of calcium oxide and 5Kg of water are added and stirred for 30min. 5Kg of formic acid, 5Kg of acetic acid, then followed by addition of 5Kg of acetic acid over 30min60Kg of monoalkyl benzenesulfonic acid, 45Kg of dialkyl benzenesulfonic acid and 45Kg of petroleum sulfonic acid are dropwise added, the sulfonic acid is dropwise added within 75-90min at a constant speed, and then 30Kg of polyisobutylene succinic anhydride is dropwise added, and the temperature is raised to 80-85 ℃. And (5) performing neutralization reaction for 1.5h, and recording the pH value of a neutralization reaction solution. Reducing the temperature to 50-55 ℃, then adding 40Kg of calcium oxide and 10Kg of water, carrying out carbonization reaction at 40-45 ℃, introducing carbon dioxide at the air speed of 350g/min, introducing air to 21Kg, adding 40Kg of calcium oxide and 10Kg of water again when the temperature is kept unchanged, and then introducing air to 42Kg, wherein the concentration of the secondary free alkali is 49mgKOH/g. Then heating to remove alcohol, water and solvent, and cooling the material to 80-85 ℃. Adding 300Kg of solvent, 80Kg of alcohol, 45Kg of calcium oxide, and 12Kg of water again, introducing carbon dioxide at a gas flow rate of 200g/min at 45-50 ℃ to 84Kg, and introducing three times of free alkali to 22mgKOH/g. And after the carbonization is finished, dealcoholizing water to 120 ℃, then precipitating and filtering, and then carrying out reduced pressure distillation on the filtrate to remove the solvent. The base number of the product is 416mgKOH/g, and the kinematic viscosity at 100 ℃ is 79mm 2 And/s, the DBN of the finished product is 18mgKOH/g, and the precipitation value is 0.07.
Example 4
300Kg of solvent, 180Kg of base oil and 50Kg of alcohol are put into a 1000L reaction kettle and stirred for 20min to be uniformly mixed. Then 20Kg of calcium oxide and 5Kg of water are added and stirred for 30min. 5Kg of formic acid and 5Kg of acetic acid are dripped in 30min, then 90Kg of monoalkyl benzene sulfonic acid, 45Kg of dialkyl benzene sulfonic acid and 15Kg of petroleum sulfonic acid are dripped in turn, the uniform dripping of sulfonic acid is finished in 75-90min, and then 30Kg of polyisobutylene succinic anhydride is dripped, and the temperature is raised to 80-85 ℃. And (5) neutralizing for 1.5h, and recording the pH value of a neutralization reaction solution. Then 40Kg of calcium oxide and 10Kg of water are added, carbon dioxide is introduced at 80-85 ℃ and at a gas speed of 350g/min to 21Kg, the free alkali in the first reaction solution is 29mgKOH/g, 40Kg of calcium oxide and 10Kg of water are added again while maintaining the temperature, then 42Kg of air is introduced, and the second free alkali is 41mgKOH/g. Then heating to remove alcohol, water and solvent, and cooling the material to 50-55 ℃. Adding 300Kg of solvent, 80Kg of alcohol, 45Kg of calcium oxide, and 12Kg of water again, introducing carbon dioxide at a gas rate of 200g/min at 45-50 deg.C to 84Kg, and introducing three times of free alkali at 18mgKOH/g. After the carbonization is finished, dealcoholizing water to 120 ℃, then precipitating, filtering, and finally obtaining the productAnd distilling the filtrate under reduced pressure to remove the solvent. The base number of the product is 414mgKOH/g, and the kinematic viscosity at 100 ℃ is 96mm 2 (s), DBN of the finished product was 57mgKOH/g, and the precipitation number was 0.05.
The data of the 4 examples and domestic calcium sulfonate samples are shown in table 1.
TABLE 1
Specifically, although the air flow rates in examples 1 to 4 were uniform, in example 1, the alkali number and DBN of the product were relatively low because a large amount of carbon dioxide was added during the secondary carbonization reaction and the colloid of calcium sulfonate was destroyed. In the sulfonic acid added in the embodiment 3, the amount of the alkylbenzene sulfonic acid is small, so that the base number and the DBN of the product are low. The base numbers and DBNs of the products of examples 2 and 4 are relatively high.
Composite calcium sulfonate grease was prepared according to the calcium sulfonate samples in the table, the preparation method comprising:
adding 400g of high-base-number calcium sulfonate, 1.0g of nano calcium carbonate and 250g of 150BS mineral oil, mixing and stirring to 85-90 ℃, and sequentially adding 40g of water, 25g of n-butanol, 6.0g of acetic acid and 3.5g of dodecylbenzene sulfonic acid. Stirring for 40min until the material becomes thick and is transformed, continuing heating to 110 ℃ after the reaction is finished, and dehydrating for 60min at the temperature. Then cooling to 90-95 ℃, sequentially adding 80g of 25% calcium hydroxide suspension by mass, stirring for 20min, adding 22g of dodecahydroxystearic acid, stirring for 20min,50g of 25% boric acid hot water solution by mass, and continuously stirring for 60min to form grease. Heating to 200g, refining at high temperature for 30min, adding 300g of 150BS base oil, quenching, stirring, cooling to 90-95 ℃, sequentially adding 1.0g of diisooctyl diphenylamine, 1.2g of molybdenum dialkyl dithiocarbamate, 2.0 g of zinc dialkyl dithiophosphate and 4.0g of octadecylamine, mixing and stirring for 60min, and then processing by a homogenizer to obtain the compound calcium sulfonate product.
The evaluation data of the complex calcium sulfonate grease prepared according to different calcium sulfonate samples are shown in table 2.
TABLE 2
The data in the table show that the sulfonate finished product has high free alkali, and the prepared finished product of the composite calcium sulfonate-based lubricating grease has obvious advantages in the aspects of dropping point, cone penetration, working cone penetration extension, copper sheet corrosion, steel mesh oil separation, sintering load and the like.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A preparation method of high-DBN calcium sulfonate for lubricating grease is characterized by comprising the following steps:
under the condition of protecting gas, adding 250-350 parts of solvent, 150-200 parts of base oil and 30-70 parts of alcohol into a reaction vessel, and stirring for 20min;
after uniformly stirring, adding 20-30 parts of calcium oxide and 3-10 parts of water into the reaction vessel, and stirring for 30min;
then dropwise adding 30-60 parts of carboxylic acid compound into the reaction container;
82-155 parts of sulfonic acid is dropwise added into the reaction container at a constant speed for 60-90min;
after the dropwise addition is finished, dropwise adding 30-40 parts of polyisobutylene succinic anhydride, heating to 80-85 ℃ for neutralization reaction, measuring the pH value of the reaction solution by using a pH meter after the reaction is carried out for 1.5h, and controlling the pH value to be more than 10;
after the neutralization reaction is finished, adding 40-50 parts of calcium oxide and 10-20 parts of water into the reaction container, heating to 80-85 ℃, and introducing carbon dioxide into the reaction container at a gas speed of 350g/min for carbonization reaction;
after the primary carbonization reaction is finished, keeping the temperature unchanged, continuously adding 40-50 parts of calcium oxide and 10-20 parts of water into the reaction container, and continuously introducing carbon dioxide into the reaction container to perform a secondary carbonization reaction;
after the secondary carbonization reaction is finished, heating to remove alcohol, water and solvent, and cooling to 50-55 ℃;
adding 40-80 parts of alcohol, 40-50 parts of calcium oxide, 10-20 parts of water and 250-350 parts of solvent into the reaction container, cooling to 45-50 ℃, and continuously introducing carbon dioxide into the reaction container at the air speed of 200g/min to perform carbonization reaction for three times;
after the third carbonization reaction is finished, removing alcohol and water, settling and separating, and centrifuging and distilling the upper-layer reaction liquid under reduced pressure to obtain a calcium sulfonate product;
wherein the mass ratio of calcium oxide to carbon dioxide in the primary carbonization reaction and the secondary carbonization reaction is 1:0.45-1:0.55; the mass ratio of calcium oxide to carbon dioxide in the third carbonization reaction is 1:0.85-1:0.95; the sulfonic acid is composed of alkyl benzene sulfonic acid and petroleum sulfonic acid, and the mass ratio of the alkyl benzene sulfonic acid to the petroleum sulfonic acid is 7:3; the carboxylic acid compound consists of formic acid and acetic acid.
2. The method for preparing high-DBN calcium sulfonate for lubricating grease according to claim 1, wherein the alcohol is one or more of C1-C8 alcohol;
the base oil is one or more of 100N, 100SN, 150N, 150SN, 500N, 500SN and 150 BS;
the solvent is one or more of benzene, toluene, xylene, 120# solvent, 200# solvent, petroleum ether, n-hexane and n-heptane.
3. The method for producing a calcium high-DBN sulfonate for a grease according to claim 1, wherein the carbon chain of the alkylbenzene sulfonic acid has C12 to C30 carbon atoms.
4. The method for producing a calcium high-DBN sulfonate for a grease according to claim 3, wherein the carbon chain of the alkylbenzene sulfonic acid has C18 to C24 carbon atoms.
5. The method for producing a calcium high-DBN sulfonate for a grease according to claim 4, wherein the carbon chain of the alkylbenzene sulfonic acid has C22 to C24 carbon atoms.
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| CN202110777408.XA CN113528215B (en) | 2021-07-09 | 2021-07-09 | Preparation method of high-DBN calcium sulfonate for lubricating grease |
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| CN202110777408.XA CN113528215B (en) | 2021-07-09 | 2021-07-09 | Preparation method of high-DBN calcium sulfonate for lubricating grease |
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