CN101885677A - Preparation method for high-alkaline calcium naphthenate - Google Patents
Preparation method for high-alkaline calcium naphthenate Download PDFInfo
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Abstract
The invention relates to a preparation method for high-alkaline calcium naphthenate. In the method, calcium hydroxide and calcium oxide are taken as calcifying agents, pure water is replaced by alkaline aqueous solution, and a mode of multiple addition is adopted to prepare a calcium naphthenate product with the base number of more than or equal to 350 mgKOH/g. The product has the advantages of low viscosity and turbidity and better high temperature cleanliness.
Description
Technical field
The present invention relates to a kind of preparation method of highly basic calcium naphthenate.
Background technology
Highly basic calcium naphthenate has good detergent-dispersant performance, oil soluble, diffustivity and acid neutralization capacity, is the detergent-dispersant additive of excellent performance, and it is widespread use in medium-to-high grade I. C. engine oil not only, especially the improvement in performance agent of marine cylinder oil first-selection.
" refining of petroleum " 1991 the 4th phases have been reported " development of DN250 highly basic calcium naphthenate and application ", and it mixes naphthenic acid, thinning oil, gasoline, water, methyl alcohol and lime, carries out neutralization reaction; Behind the secondary calcify reaction, deviate from promotor and water, filter the back steaming and desolventize, obtaining base number is the calcium naphthenate product of 250mgKOH/g.
Chinese patent CN1216027C has introduced the preparation method of naphthenate with superhigh base number calcium, this method is with after carrying out neutralization reaction in naphthenic acid, solvent, calcium hydroxide, the water input reactor, drop into methyl alcohol and low mass molecule alcohol promotor, feed carbonic acid gas and carry out carbonation reaction, and divide and drop into remaining calcium hydroxide 2～4 times, control reaction end by measured reaction liquid pH value, after reaction is finished, add flocculating aids, the pressure filtration slagging-off steams solvent and promptly obtains desired product.Can synthesize the naphthenate with superhigh base number calcium product of base number with this method greater than 400mgKOH/g,
Mainly there is following problem in prior art: the one, the acidity of macromolecule naphthenic acid a little less than, neutralization reaction the difficulty; The 2nd, calcium hydroxide is assembled the sedimentation slagging easily in the many environment of water, thereby can reduce the base number of product, and viscosity and turbidity are increased; The 3rd, reaction end is wayward, CO
2One is excessive slightly, and the product colloidal structure will be destroyed, produces precipitation in a large number.
Summary of the invention
The invention provides a kind of preparation method of highly basic calcium naphthenate, this method not only can overcome the problem that above-mentioned prior art exists, and can access the better calcium naphthenate product of high temperature detergent performance.
Among the present invention, except that specifying, all raw material consumptions are 100 parts in the weight of naphthenic acid all.
Method provided by the present invention comprises:
(1) varsol, neutral oil, alkaline aqueous solution, calcium hydroxide are mixed with naphthenic acid, carry out neutralization reaction, the consumption of alkaline aqueous solution is 5～20 parts;
(2) add promotor;
(3) add calcium oxide and alkaline aqueous solution, feed carbonic acid gas and carry out carbonation reaction, carbonic acid gas feeding amount is 60～140% of a theoretical value, and the consumption of alkaline aqueous solution is 2～20 parts;
(4) step (3) is repeated 1～2 time;
(5) deviate from alcohol, water, solvent, promotor and solid residue after, obtain product;
Described alkaline aqueous solution is selected from one or more in ammonia soln, alkali metal hydroxide aqueous solution and the alkaline earth metal hydroxides aqueous solution.
The concentration of described alkaline aqueous solution is preferably 5wt%～35wt%.
Described varsol can be alkane, aromatic hydrocarbons or the mixture of the two, is preferably boiling range one or more in 60 ℃～180 ℃ straight-run spirit, benzene, toluene and dimethylbenzene.The effect of solvent is the place that a reaction is provided for the reaction of neutralization reaction and high basicity.
Described neutral oil is that kinematic viscosity (40 ℃) is 10～50mm
2The lubricant base of/S; Be preferably 100SN or 150SN.The effect of neutral oil is the place that a stable dispersion is provided to final product.
The weight-average molecular weight of described naphthenic acid is 250～650, is preferably 300～500.
In the step (1), the varsol consumption is 50～450 parts, is preferably 100～300 parts; The neutral oil consumption is 30～300 parts, is preferably 50～200 parts; The consumption of calcium hydroxide is 5～35 parts, is preferably 10～25 parts; Temperature of reaction is 45～60 ℃, and the reaction times is 30～90min.
Adopt all promotor of the prior art all can realize the present invention, but when adopting the combination of methyl alcohol and propyl carbinol, resulting calcium naphthenate product have optimum properties.The weight ratio of methyl alcohol and propyl carbinol is 1: 0.5～1.5, be preferably 1: 0.8～and 1.2.
In the step (2), the consumption of promotor is 10～130, is preferably 20～90 parts.
Described calcium hydroxide and calcium oxide both can be analytical pure, also can be technical pures.
In the step (3), the consumption of calcium oxide is 10～30 parts; Temperature of reaction is 45～60 ℃.
In the step (3), the feeding speed of carbonic acid gas is preferably 0.5～2.0ml/ming.
Theoretical value in the step (3) is calculated and is got with the calcium oxide content of each adding.
Step also can add alkali metal chloride and/or alkaline earth metal chloride in (2), in preferred sodium-chlor, Repone K, magnesium chloride and the calcium chloride one or more.The consumption of alkali metal chloride and/or alkaline earth metal chloride is 1～15 part, is preferably 4～12 parts.Adding alkali metal chloride and/or alkaline earth metal chloride help avoid owing to carbonic acid gas is excessive and produce precipitation, and the terminal point control of carbonation reaction is more prone to.
The present invention has following useful technique effect:
(1) the present invention adopts gradation to add the mode of alkaline aqueous solution, not only helps neutralization reaction, and helps to improve the detergency of product, can also avoid the gathering settlement issues of calcium hydroxide.
(2) to adopt calcium oxide be calcification reagent in the present invention, helps improving the carbonation reaction activity.
(3) the present invention adds alkali metal chloride and/or alkaline earth metal chloride the terminal point control of carbonation reaction is more prone to.
(4) method of the present invention can obtain the better calcium naphthenate product of over-all properties.Base number 〉=the 350mgKOH/g of this product, viscosity and turbidity are low, and colloidal stability and high temperature detergent performance are better.
Embodiment
Further set forth the present invention by the following examples.
Embodiment 1
In reactor, add 150 milliliters of 120# industrial napthas, 150SN neutral oil 35 grams, ammonia soln 6 grams of 10wt%, calcium hydroxide 10 grams, naphthenic acid raw material 65 grams (pure acid number 118mgKOH/g, acid content 72%), control reaction temperature is at 45～60 ℃, behind the neutralization reaction 60min, generate neutral calcium naphthenate.Add 10 gram calcium oxide, 20 gram methyl alcohol, 20 gram propyl carbinols, the ammonia soln of 4 gram 10wt%, the NaCl aqueous solution of 4 gram 25wt%, feed carbonic acid gas, Ventilation Rate is about 80ml/min, and the feeding amount reaches 70% o'clock of theoretical value, the ammonia soln that adds 10 gram calcium oxide and 3 gram 10wt%, feed carbonic acid gas and carry out the secondary carbonation reaction, when the specific absorption of carbonic acid gas reached 80%, reaction finished.After carbonating finishes, be warmed up to 120 ℃ of distillation dealcoholysis, water.Add 100 milliliters of gasoline in the material that obtains, put into whizzer then, 4000rpm is centrifugal with rotating speed, flash distillation thing after centrifugal is put into the matrass that has decompression facility, at first be warmed up to 120 ℃ of air distillations, 5 ℃/min of heat-up rate, constant temperature 30min, carry out underpressure distillation to system then, vacuum degree control is more than 0.02Mpa.Temperature is controlled at 150 ℃, and constant temperature 30min obtains product A 1 at last.
Embodiment 2
In reactor, add 150 milliliters of toluene, 150SN neutral oil 35 grams, potassium hydroxide aqueous solution 6 grams of 10wt%, calcium hydroxide 10 grams, naphthenic acid raw material 65 grams (pure acid number 118mgKOH/g, acid content 72%), control reaction temperature is at 45～60 ℃, behind the neutralization reaction 60min, generate neutral calcium naphthenate.Add 10 gram calcium oxide, 20 gram methyl alcohol, 20 gram propyl carbinols, the potassium hydroxide aqueous solution of 2 gram 10wt%, the NaCl methanol solution of 4 gram 25wt%, feed carbonic acid gas, Ventilation Rate is about 80ml/min, and the feeding amount reaches 70% o'clock of theoretical value, the potassium hydroxide aqueous solution that adds 10 gram calcium oxide and 2 gram 10wt%, feed carbonic acid gas and carry out the secondary carbonation reaction, when the specific absorption of carbonic acid gas reached 80%, reaction finished.Carbonating is warmed up to 120 ℃ of dealcoholysis, water after finishing.Add 100 milliliters of gasoline in the material that obtains, put into whizzer then, 4000rpm is centrifugal with rotating speed, flash distillation thing after centrifugal is put into the matrass that has decompression facility, at first be warmed up to 120 ℃ of air distillations, 5 ℃/min of heat-up rate, constant temperature 30min, carry out underpressure distillation to system then, vacuum degree control is more than 0.02Mpa.Temperature is controlled at 150 ℃, and constant temperature 30min obtains product A 2 at last.
Comparative Examples 1
In reactor, add 150 milliliters of 120# industrial napthas, 150SN neutral oil 35 grams, calcium hydroxide 10 grams, naphthenic acid raw material 65 grams (pure acid number 118mgKOH/g, acid content 72%), water 13 grams, control reaction temperature behind the neutralization reaction 60min, generates neutral calcium naphthenate at 45～60 ℃.Add 10 gram calcium hydroxides, 30 gram methyl alcohol feed carbonic acid gas, Ventilation Rate is about 80ml/min, and the feeding amount reaches 70% o'clock of theoretical value, adds 10 gram calcium hydroxides, feed carbonic acid gas and carry out the secondary carbonation reaction, when the specific absorption of carbonic acid gas reached 80%, reaction finished.Carbonating is warmed up to 120 ℃ of dealcoholysis, water after finishing.Add 100 milliliters of gasoline in the material that obtains, put into whizzer then, 4000rpm is centrifugal with rotating speed, flash distillation thing after centrifugal is put into the matrass that has decompression facility, at first be warmed up to 120 ℃ of air distillations, 5 ℃/min of heat-up rate, constant temperature 30min, carry out underpressure distillation then, vacuum degree control is more than 0.02Mpa.Temperature is controlled at 150 ℃, and constant temperature 30min obtains product B 1 at last.
Comparative Examples 2
In reactor, add 150 milliliters of 120# industrial napthas, 150SN neutral oil 35 grams, calcium hydroxide 10 grams, naphthenic acid raw material 65 grams (pure acid number 118mgKOH/g, acid content 72%), water 13 grams, control reaction temperature behind the neutralization reaction 60min, generates neutral calcium naphthenate at 45～60 ℃.Add 10 gram calcium hydroxides, 20 gram methyl alcohol, 20 gram propyl carbinols, feed carbonic acid gas, Ventilation Rate is about 80ml/min, and the feeding amount reaches 70% o'clock of theoretical value, add 10 gram calcium hydroxides, feed carbonic acid gas and carry out the secondary carbonation reaction, when the specific absorption of carbonic acid gas reached 80%, reaction finished.Carbonating is warmed up to 120 ℃ of dealcoholysis, water after finishing.Add 100 milliliters of gasoline in the material that obtains, put into whizzer then, 4000rpm is centrifugal with rotating speed, flash distillation thing after centrifugal is put into the matrass that has decompression facility, at first be warmed up to 120 ℃ of air distillations, 5 ℃/min of heat-up rate, constant temperature 30min, carry out underpressure distillation to system then, vacuum degree control is more than 0.02Mpa.Temperature is controlled at 150 ℃, and constant temperature 30min obtains product B 2 at last.
The product and the commercially available prod T114 of embodiment and Comparative Examples are carried out assay, the results are shown in Table 1.
Table 1
The coking experiment condition: plate temperature/oil temperature=320 ℃/100 ℃, the time is 2 hours, stops/open=45 seconds/15 seconds.
The lacquering experiment condition: plate temperature/oil temperature=300 ℃/150 ℃, the time is 4 hours, continuously.
As can be seen from Table 1, the resulting calcium naphthenate product of method of the present invention, base number height, viscosity and turbidity are low, and high temperature detergency is better.
Claims (13)
1. the preparation method of a highly basic calcium naphthenate comprises:
(1) varsol, neutral oil, alkaline aqueous solution, calcium hydroxide are mixed with naphthenic acid, carry out neutralization reaction, the consumption of alkaline aqueous solution is 5～20 parts;
(2) add promotor;
(3) add calcium oxide and alkaline aqueous solution, feed carbonic acid gas and carry out carbonation reaction, carbonic acid gas feeding amount is 60～140% of a theoretical value, and the consumption of alkaline aqueous solution is 2～20 parts;
(4) step (3) is repeated 1～2 time;
(5) deviate from alcohol, water, solvent, promotor and solid residue after, obtain product;
Wherein, alkaline aqueous solution is selected from one or more in ammonia soln, alkali metal hydroxide aqueous solution and the alkaline earth metal hydroxides aqueous solution; The raw material consumption is 100 parts in naphthenic acid weight all.
2. in accordance with the method for claim 1, it is characterized in that the weight-average molecular weight of described naphthenic acid is 250～650.
3. in accordance with the method for claim 1, it is characterized in that described varsol is boiling range one or more in 60 ℃～180 ℃ straight-run spirit, benzene, toluene and dimethylbenzene.
4. in accordance with the method for claim 1, it is characterized in that described neutral oil is 100SN or 150SN.
5. in accordance with the method for claim 1, it is characterized in that the consumption of varsol is 50～450 parts, the consumption of neutral oil is 30～300 parts, and the consumption of calcium hydroxide is 5～35 parts.
6. in accordance with the method for claim 1, it is characterized in that the concentration of described alkaline aqueous solution is 5wt%～35wt%.
7. in accordance with the method for claim 1, it is characterized in that promotor is methyl alcohol and propyl carbinol, the weight ratio of the two is 1: 0.5～1.5.
8. in accordance with the method for claim 1, it is characterized in that the consumption of promotor is 10～130 parts.
9. in accordance with the method for claim 1, it is characterized in that in the step (3), the consumption of calcium oxide is 10～30 parts.
10. in accordance with the method for claim 1, it is characterized in that in the step (3), the feeding speed of carbonic acid gas is 0.5～2.0ml/ming.
11. in accordance with the method for claim 1, it is characterized in that, add alkali metal chloride and/or alkaline earth metal chloride in the step (2).
12. in accordance with the method for claim 1, it is characterized in that the consumption of alkali metal chloride and/or alkaline earth metal chloride is 1～15 part.
13. the calcium naphthenate product that makes according to either party's method in the claim 1～12.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104293449A (en) * | 2013-07-17 | 2015-01-21 | 中国石油化工股份有限公司 | Composite calcium naphthenate-based 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 |
| 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 |
| CN115806353A (en) * | 2021-09-13 | 2023-03-17 | 中国石油化工股份有限公司 | Method for continuously carbonating SEBS (styrene-ethylene-butadiene-styrene) desalination wastewater and extracting and recycling neodecanoic acid |
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| CN1465560A (en) * | 2002-06-28 | 2004-01-07 | 中国石油天然气股份有限公司 | Preparation method of ultrahigh-alkalinity calcium naphthenate |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN104293449A (en) * | 2013-07-17 | 2015-01-21 | 中国石油化工股份有限公司 | Composite calcium naphthenate-based 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 |
| CN104293449B (en) * | 2013-07-17 | 2016-08-10 | 中国石油化工股份有限公司 | A kind of Composite calcium naphthenate base grease and preparation method thereof |
| 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 |
| 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 |
| CN115806353A (en) * | 2021-09-13 | 2023-03-17 | 中国石油化工股份有限公司 | Method for continuously carbonating SEBS (styrene-ethylene-butadiene-styrene) desalination wastewater and extracting and recycling neodecanoic acid |
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