CN1465560A - Process for preparing ultrahigh basicity calcium naphthenate - Google Patents
Process for preparing ultrahigh basicity calcium naphthenate Download PDFInfo
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- CN1465560A CN1465560A CNA021237808A CN02123780A CN1465560A CN 1465560 A CN1465560 A CN 1465560A CN A021237808 A CNA021237808 A CN A021237808A CN 02123780 A CN02123780 A CN 02123780A CN 1465560 A CN1465560 A CN 1465560A
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Abstract
The preparation method of ultrahigh basic calcium naphthenate uses the naphthenic acid and calcium hydroxide as raw material, in the prssence of methyl alcohol and activating accelerator the ultrahigh basic number calcium naphthenate whose basic number is greater than 400 mg KOH/g can be synthesized, the end of carbonization reaction can be controlled by pH value of reaction solution, after thr eaction is completed, the filter adjuvant can be added, pressurized, filtered and the residue is removed, and the solvent is removed by evaporation so as to obtain the invented required product.
Description
Relate to the field
The present invention relates to a kind of peace and quiet dispersing additive that is used for internal combustion (IC) engine lubricating oil and preparation method thereof, belong to the lubricating oil field, specifically, is process for preparing ultrahigh basicity calcium naphthenate.
Background technology
Highly basic calcium naphthenate has detergent-dispersant performance preferably, and good acid neutralization capacity has excellent diffustivity, thereby is mainly used in the production marine cylinder oil.1991 the 4th phases of " refining of petroleum " magazine have reported that base number is the calcium naphthenate product development method of 250mgKOH/g, use methyl alcohol as promotor, the calcium naphthenate product of preparation base number 250mgKOH/g.
Technology contents
The objective of the invention is to provide a kind of naphthenate with superhigh base number calcium preparation method, a kind of peace and quiet dispersing additive of excellent property is provided for lubricating oil, under the identical condition of lubricating oil base number, can reduce the dosage of the quiet dispersion agent of metal, have favorable economic benefit and social benefit.
The method for preparing ultrahigh basicity calcium naphthenate of the present invention is as follows:
Naphthenic acid, solvent and the calcium hydroxide of metering are mixed stirring and is warming up to 40 ℃ in container; Drop into water, keep temperature of reaction between 50～65 ℃, neutralization reaction 1 hour; Drop into methyl alcohol and accelerant A, neutralization reaction 1～2 hour; Drop into the calcium hydroxide of residual content several times, the back that stirs feeds carbon dioxide, carries out carbonation reaction, keeps the carbonation reaction temperature at 50～60 ℃, is 8～11 up to the pH of reaction solution value, stops carbonation reaction; Be warming up to more than 120 ℃, promotor and water are removed in distillation; Add flocculating aids, remove solid slag through pressure filtration; Underpressure distillation removes to desolvate and obtains product.
Said neutralization reaction of the present invention and carbonation reaction, the proportion scale of each component is: in 100 parts of naphthenic acid, calcium hydroxide is 40～70 parts, methyl alcohol is 10～50 parts, accelerant A is 5～20 parts, and water is 0.5～10 part, and solvent is 50～200 parts, flocculating aids is 3～50 parts, and carbonic acid gas ventilation speed is 30mL/min.
The mixture that the said reaction raw materials naphthenic acid of the present invention is naphthenic acid, mineral lubricating oils etc., naphthenic acid content is preferably between 30～50% (weights) between 20～70% (weights).
The acidic components of the said naphthenic acid of the present invention for from the fraction oil that crude distillation obtains, extracting, structural formula is:
Wherein, n=7～36, (CH2)
nIn also may comprise 1～4 five-ring or six-ring, R is the alkyl chain of C3～20;
The temperature of said neutralization reaction of the present invention and carbonation reaction is controlled at 30～70 ℃, is preferably between 50～65 ℃.
The said carbon dioxide feeding of the present invention speed is 10～200 milliliters/min of per 100 gram naphthenic acid per minutes, is preferably 30～50 milliliters/min.
The terminal point of the said carbonation reaction of the present invention is with the pH value control of reaction solution, and the general pH value is controlled between 8～12, is preferably 9～11.
The said accelerant A of the present invention is C
4-8Low mass molecule alcohol or its mixture, for example, the mixture of butanols, amylalcohol, hexanol, enanthol and octanol, add-on is 5～20 parts, is preferably 8～15 parts.
The said solvent of the present invention can be hydro carbons or aromatic hydrocarbon solvent, for example, gasoline, dimethylbenzene, add-on is 50～300 parts, is preferably 70～200 parts.
The said flocculating aids of the present invention can be diatomite or light calcium carbonate, and add-on is 3～50 parts, is preferably 8～15 parts.
The purity of the said calcium hydroxide of the present invention is not less than 95%.The add-on of calcium hydroxide is 3～10 parts in neutralization reaction, drops into the calcium hydroxide of residual content in carbonation reaction.
Concrete enforcement
The following examples will be made further supplementary notes to the present invention.
The analytical procedure of every index in the embodiment of the invention:
1, total basicnumber analytical procedure: SH/T0251.
2, viscosity analytical procedure: GB/T265.
3, calcium contents analytical procedure: SH/T0297
Embodiment 1:
In having 2000 milliliters of there-necked flasks of electronic stirring, condensation water trap, drop into 300 gram naphthenic acid (pure acid number 115.8mgKOH/g, acid content 45%) and 300 the gram dimethylbenzene, add 15.0 gram calcium hydroxides (purity 98.12%) and 6.0 gram water, holding temperature was carried out neutralization reaction 1 hour about 60 ℃; Add 45 gram methyl alcohol, 33.0 gram n-hexyl alcohols and 45.0 gram calcium hydroxides, feeding flow velocity is the carbonic acid gas of 100 ml/min, carries out carbonation reaction, to the pH value of reaction solution be 11.0; Stop carbonic acid gas, add 45.0 gram calcium hydroxides, feed carbonic acid gas, continue carbonation reaction, to the pH value of reaction solution be 11.0; Stop carbonic acid gas, add 40.0 gram calcium hydroxides, to the pH value of reaction solution be 10.0, stop carbonation reaction.Be warming up to 120 ℃ of steaming engaging benzenemethanols and water, add the light calcium carbonate flocculating aidss of 45 grams, pressure filtration, filtrate is removed removal xylene and butanols gets product through underpressure distillation.Filtration velocity kg/m
2.h the product calcium contents 14.5%, base number 408.2mgKOH/g.
Embodiment 2:
In having 2000 milliliters of there-necked flasks of electronic stirring, condensation water trap, drop into 300 gram naphthenic acid (pure acid number 115.8mgKOH/g, acid content 45%) and 300 the gram dimethylbenzene, add 15.0 gram calcium hydroxides (purity 98.12%) and 6.0 gram water, holding temperature was carried out neutralization reaction 1 hour about 60 ℃; Add 33.0 gram butanols and 45.0 gram calcium hydroxides, feeding flow velocity is the carbonic acid gas of 100 ml/min, carries out carbonation reaction, to the pH value of reaction solution be 11.0; Stop carbonic acid gas, add 45.0 gram calcium hydroxides, feed carbonic acid gas, continue carbonation reaction, to the pH value of reaction solution be 11.0; Stop carbonic acid gas, add 40.0 gram calcium hydroxides, to the pH value of reaction solution be 10.0, stop carbonation reaction.Be warming up to 120 ℃ of steaming engaging benzenemethanols and water, add the light calcium carbonate flocculating aidss of 45 grams, pressure filtration, filtrate is removed removal xylene and butanols gets product through underpressure distillation.Product calcium contents 14.6%, base number 406.8mgKOH/g.
Embodiment 3:
In having 2000 milliliters of there-necked flasks of electronic stirring, condensation water trap, drop into 300 gram naphthenic acid (pure acid number 115.8mgKOH/g, acid content 45%) and 300 the gram dimethylbenzene, add 15.0 gram calcium hydroxides (purity 99%) and 6.0 gram water, holding temperature was carried out neutralization reaction 1 hour about 60 ℃; Add 33.0 industrial octanols of gram and 45.0 gram calcium hydroxides, feeding flow velocity is the carbonic acid gas of 100 ml/min, carries out carbonation reaction, to the pH value of reaction solution be 11.0; Stop carbonic acid gas, add 45.0 gram calcium hydroxides, feed carbonic acid gas, continue carbonation reaction, to the pH value of reaction solution be 11.0; Stop carbonic acid gas, add 40.0 gram calcium hydroxides, to the pH value of reaction solution be 10.0, stop carbonation reaction.Be warming up to 120 ℃ of steaming engaging benzenemethanols and water, add the light calcium carbonate flocculating aidss of 45 grams, pressure filtration, filtrate is removed removal xylene and butanols gets product through underpressure distillation.Product calcium contents 14.6%, base number 418.6mgKOH/g.
Embodiment 4:
In having 2000 milliliters of there-necked flasks of electronic stirring, condensation water trap, drop into 300 gram naphthenic acid (pure acid number 155.8mgKOH/g, acid content 45%) and 300 the gram dimethylbenzene, add 15.0 gram calcium hydroxides (purity 99%) and 6.0 gram water, holding temperature was carried out neutralization reaction 1 hour about 60 ℃; Add 33.0 gram butanols and 45.0 gram calcium hydroxides, feeding flow velocity is the carbonic acid gas of 100 ml/min, carries out carbonation reaction, to the pH value of reaction solution be 11.0; Stop carbonic acid gas, add 45.0 gram calcium hydroxides, feed carbonic acid gas, continue carbonation reaction, to the pH value of reaction solution be 11.0; Stop carbonic acid gas, add 40.0 gram calcium hydroxides, to the pH value of reaction solution be 10.0, stop carbonation reaction.Be warming up to 120 ℃ of steaming engaging benzenemethanols and water, add the light calcium carbonate flocculating aidss of 45 grams, pressure filtration, filtrate is removed removal xylene and butanols gets product through underpressure distillation.Product calcium contents 13.9%, base number 434.1mgKOH/g.
Embodiment 5:
In having 2000 milliliters of there-necked flasks of electronic stirring, condensation water trap, drop into 300 gram naphthenic acid (pure acid number 198.7mgKOH/g, acid content 45%) and 300 the gram dimethylbenzene, add 15.7 gram calcium hydroxides (purity 99%) and 6.0 gram water, holding temperature was carried out neutralization reaction 1 hour about 60 ℃; Add 33.0 gram butanols and 45.0 gram calcium hydroxides, feeding flow velocity is the carbonic acid gas of 100 ml/min, carries out carbonation reaction, to the pH value of reaction solution be 11.0; Stop carbonic acid gas, add 45.0 gram calcium hydroxides, feed carbonic acid gas, continue carbonation reaction, to the pH value of reaction solution be 11.0; Stop carbonic acid gas, add 40.0 gram calcium hydroxides, to the pH value of reaction solution be 10.0, stop carbonation reaction.Be warming up to 120 ℃ of steaming engaging benzenemethanols and water, add the light calcium carbonate flocculating aidss of 45 grams, pressure filtration, filtrate is removed removal xylene and butanols gets product through underpressure distillation.Product calcium contents 15.4%, base number 438mgKOH/g.
Claims (13)
1. the preparation method of a ultrahigh basicity calcium naphthenate is characterized in that:
(a) naphthenic acid, solvent and the calcium hydroxide with metering mixes stirring and is warming up to 30～60 ℃ in container;
(b) drop into water, keep temperature of reaction between 30～70 ℃, neutralization reaction 0.5～3 hour;
(c) drop into methyl alcohol and accelerant A, neutralization reaction 0.5～3 hour;
(d) dropping into the calcium hydroxide of residual content several times, feed carbon dioxide, carry out carbonation reaction, keep the carbonation reaction temperature at 30～70 ℃, is 8～12 up to the pH of reaction solution value, the termination carbonation reaction;
(e) be warming up to more than 120 ℃, promotor and water are removed in distillation; Add flocculating aids, remove solid slag through pressure filtration; Underpressure distillation removes to desolvate and obtains product.
2. method according to claim 1, it is characterized in that: the ratio that participates in each component batching of neutralization reaction and carbonation reaction is, in 100 parts of naphthenic acid, calcium hydroxide is 40～70 parts, methyl alcohol is 10～50 parts, and accelerant A is 5～20 parts, and water is 0.5～10 part, solvent is 50～200 parts, and flocculating aids is 3～50 parts.
3. method according to claim 1 and 2 is characterized in that: the reaction raw materials naphthenic acid is the mixture of naphthenic acid, mineral lubricating oils, and pure acid content is between 30～60%.
4. method according to claim 1 and 2 is characterized in that: described calcium hydroxide purity is more than 95%.
5. claim 1 or 2 described methods, it is characterized in that: in 100 parts of naphthenic acid, the required calcium hydroxide of neutralization reaction is 10～25 parts.
6. method according to claim 1 and 2 is characterized in that: carbonation reaction calcium hydroxide divides 2～4 addings.
7. method according to claim 1 and 2 is characterized in that: the consumption of methyl alcohol is 10～50 parts.
8. method according to claim 1 is characterized in that: described accelerant A is low mass molecule alcohol or its mixture of C4～C8, and the accelerant A add-on is 5～30 parts.
9. method according to claim 1 and 2 is characterized in that: the water that neutralization reaction adds adds before methyl alcohol and accelerant A, and the add-on of neutralization reaction water is 0.5～10 part.
10. method according to claim 1 is characterized in that: carbon dioxide feeding speed is 10～100 milliliters of per 100 gram naphthenic acid per minutes.
12. method according to claim 1 is characterized in that: the terminal point of carbonation reaction is with the pH value control of reaction solution, and the general pH value is controlled between 7～12.
13. method according to claim 1 and 2 is characterized in that: described solvent can be alkanes or aromatic hydrocarbon solvent, can be gasoline, dimethylbenzene, and solvent adding amount is 30～500 parts, is preferably 80～200 parts.
14. method according to claim 1 is characterized in that: described flocculating aids can be diatomite or light calcium carbonate, and the flocculating aids add-on is 3～50 parts.
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| CN 02123780 CN1216027C (en) | 2002-06-28 | 2002-06-28 | Process for preparing ultrahigh basicity calcium naphthenate |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101886013A (en) * | 2009-05-14 | 2010-11-17 | 中国石油化工股份有限公司 | Method for preparing mixed-matrix metal cleaner |
| CN101885677A (en) * | 2009-05-14 | 2010-11-17 | 中国石油化工股份有限公司 | Preparation method for high-alkaline calcium naphthenate |
| CN102071085A (en) * | 2009-11-19 | 2011-05-25 | 中国石油化工股份有限公司 | High-base number metal detergent and preparation method thereof |
| CN103666647A (en) * | 2012-09-25 | 2014-03-26 | 中国石油化工股份有限公司 | High-base-number naphthenic acid composite calcium-magnesium detergent, preparation method thereof and lubricating oil composition |
| CN103666642A (en) * | 2012-09-25 | 2014-03-26 | 中国石油化工股份有限公司 | High-base-number lithium naphthenate and preparation method thereof as well as lubricating oil composition |
| CN103666641A (en) * | 2012-09-25 | 2014-03-26 | 中国石油化工股份有限公司 | High base number sodium napthionate clearing agent, and preparation method and lubricating oil composition thereof |
| CN104276945A (en) * | 2013-07-02 | 2015-01-14 | 中国科学院兰州化学物理研究所 | Preparation method boronized high-base-number calcium naphthenate |
| CN104293450A (en) * | 2013-07-17 | 2015-01-21 | 中国石油化工股份有限公司 | Composite calcium naphthenate-based tetra-polyurea lubricating grease and preparation method thereof |
| CN104449961A (en) * | 2013-09-13 | 2015-03-25 | 中国石油化工股份有限公司 | Calcium sulfonate-calcium naphthenate-based urea hexamer grease and preparation method thereof |
| CN106977393A (en) * | 2017-05-27 | 2017-07-25 | 西安石油大学 | The technique of continuous production calcium naphthenate |
| CN104449956B (en) * | 2013-09-13 | 2017-07-25 | 中国石油化工股份有限公司 | A kind of high base number composite calcium-base polyurea grease and preparation method thereof |
| CN111849587A (en) * | 2020-08-14 | 2020-10-30 | 德杰(浙江)润滑科技有限公司 | Preparation method and process of lubricating oil additive |
| CN113549481A (en) * | 2021-07-29 | 2021-10-26 | 新乡市瑞丰新材料股份有限公司 | Preparation process of ultrahigh-base-number calcium alkyl salicylate |
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2002
- 2002-06-28 CN CN 02123780 patent/CN1216027C/en not_active Expired - Fee Related
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101886013A (en) * | 2009-05-14 | 2010-11-17 | 中国石油化工股份有限公司 | Method for preparing mixed-matrix metal cleaner |
| CN101885677A (en) * | 2009-05-14 | 2010-11-17 | 中国石油化工股份有限公司 | Preparation method for high-alkaline calcium naphthenate |
| CN101886013B (en) * | 2009-05-14 | 2013-01-30 | 中国石油化工股份有限公司 | Method for preparing mixed-matrix metal cleaner |
| CN101885677B (en) * | 2009-05-14 | 2013-09-04 | 中国石油化工股份有限公司 | Preparation method for high-alkaline calcium naphthenate |
| CN102071085A (en) * | 2009-11-19 | 2011-05-25 | 中国石油化工股份有限公司 | High-base number metal detergent and preparation method thereof |
| CN102071085B (en) * | 2009-11-19 | 2013-01-30 | 中国石油化工股份有限公司 | High-base number metal detergent and preparation method thereof |
| CN103666642B (en) * | 2012-09-25 | 2016-03-23 | 中国石油化工股份有限公司 | High base number naphthenic acid lithium, its preparation method and lubricating oil composition |
| CN103666641A (en) * | 2012-09-25 | 2014-03-26 | 中国石油化工股份有限公司 | High base number sodium napthionate clearing agent, and preparation method and lubricating oil composition thereof |
| CN103666642A (en) * | 2012-09-25 | 2014-03-26 | 中国石油化工股份有限公司 | High-base-number lithium naphthenate and preparation method thereof as well as lubricating oil composition |
| CN103666647B (en) * | 2012-09-25 | 2015-07-01 | 中国石油化工股份有限公司 | High-base-number naphthenic acid composite calcium-magnesium detergent, preparation method thereof and lubricating oil composition |
| CN103666641B (en) * | 2012-09-25 | 2015-09-23 | 中国石油化工股份有限公司 | High base number sodium napthionate purification agent, its preparation method and lubricating oil composition |
| CN103666647A (en) * | 2012-09-25 | 2014-03-26 | 中国石油化工股份有限公司 | High-base-number naphthenic acid composite calcium-magnesium detergent, preparation method thereof and lubricating oil composition |
| CN104276945A (en) * | 2013-07-02 | 2015-01-14 | 中国科学院兰州化学物理研究所 | Preparation method boronized high-base-number calcium naphthenate |
| CN104276945B (en) * | 2013-07-02 | 2016-01-13 | 中国科学院兰州化学物理研究所 | A kind of preparation method of boronation overbased calcium alkyl-salicylate |
| CN104293450B (en) * | 2013-07-17 | 2017-02-08 | 中国石油化工股份有限公司 | Composite calcium naphthenate-based tetra-polyurea lubricating grease and preparation method thereof |
| CN104293450A (en) * | 2013-07-17 | 2015-01-21 | 中国石油化工股份有限公司 | Composite calcium naphthenate-based tetra-polyurea lubricating grease and preparation method thereof |
| CN104449961A (en) * | 2013-09-13 | 2015-03-25 | 中国石油化工股份有限公司 | Calcium sulfonate-calcium naphthenate-based urea hexamer grease and preparation method thereof |
| CN104449961B (en) * | 2013-09-13 | 2017-07-25 | 中国石油化工股份有限公司 | A kind of sulfoacid calcium calcium naphthenate-based hexapolyurea lubricating grease and preparation method thereof |
| CN104449956B (en) * | 2013-09-13 | 2017-07-25 | 中国石油化工股份有限公司 | A kind of high base number composite calcium-base polyurea grease and preparation method thereof |
| CN106977393A (en) * | 2017-05-27 | 2017-07-25 | 西安石油大学 | The technique of continuous production calcium naphthenate |
| CN106977393B (en) * | 2017-05-27 | 2019-04-23 | 西安石油大学 | The technique of continuous production calcium naphthenate |
| CN111849587A (en) * | 2020-08-14 | 2020-10-30 | 德杰(浙江)润滑科技有限公司 | Preparation method and process of lubricating oil additive |
| CN113549481A (en) * | 2021-07-29 | 2021-10-26 | 新乡市瑞丰新材料股份有限公司 | Preparation process of ultrahigh-base-number calcium alkyl salicylate |
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