CN102071085B - High-base number metal detergent and preparation method thereof - Google Patents
High-base number metal detergent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-base number metal detergent and a preparation method thereof. The preparation method comprises the following steps of: mixing and performing a neutralization reaction on a hydrocarbon solvent, neutral oil, naphthenic acid, water, alkylphenol and calcium hydroxide and/or calcium oxide; and adding methanol and the calcium hydroxide and/or the calcium oxide; introducing carbon dioxide to perform a carbonation reaction twice; and obtaining a product through an aftertreatment process. The product has an ultra-high base number and better anti-oxidation stability.
Description
Technical field
The present invention relates to a kind of high-base number metal detergent and preparation method thereof, specifically, is compound high-base number metal detergent of a kind of naphthenate and alkyl phenate and preparation method thereof.
Background technology
Metal detergent is one of main additive in the I. C. engine oil, by solubilising, dispersion, neutralizing effect, works with other additive one in I. C. engine oil, suppresses the generation of carbon distribution, paint film and greasy filth in the oil product, guarantees engine work.
Naphthenate is a class purification agent that occurs in history early, highly basic calcium naphthenate has stronger detergent-dispersant performance, acid neutralization capacity and good oil-soluble while, also has excellent diffusion, it not only can widespread use in the medium and high classes I. C. engine oil, especially the improvement in performance agent of high alkalinity marine cylinder oil first-selection.The Shell that Britain is arranged at present in the world, several companies such as OSCA of the Elf of France and Japan produce this product, and domestic only Dushanzi, Xinjiang petro-chemical corporation mainly contains three kinds of T112, T113 and T114 producing the calcium naphthenate series product.
Traditional naphthenate metal detergent anti-oxidative stability can be relatively poor, in use can produce catalysed oxidn to oil product, common solution is when using naphthenate, add to come the inhibited oxidation effect into some oxidation inhibitor, but the method has not only increased cost, and can bring other problems that is difficult to overcome, as other performances of product are reduced.
" refining of petroleum " the 4th phase in 1991 has been reported " development of DN250 highly basic calcium naphthenate and application ", and the method uses methyl alcohol as promotor, and can prepare base number is the calcium naphthenate product of 250mgKOH/g.Chinese patent CN1164556C, CN1216027C have introduced respectively the preparation method of magnesium naphthenate with superhigh base number and naphthenate with superhigh base number calcium.These preparation methods mainly are by selecting different promotor, improve product basic component content, thereby improve the product base number, improve product basic component content and can not significantly improve the purification agent performance and only rely on.
Summary of the invention
The technical problem to be solved in the present invention is to improve the resistance of oxidation of calcium naphthenate, and the technical problem that the present invention further will solve is to improve the base number of calcium naphthenate.
Among the present invention, except specifying, all raw material consumptions are all take naphthenic acid weight as 100 parts.
The invention provides a kind of preparation method of high-base number metal detergent, comprising:
(1) varsol, neutral oil, naphthenic acid, water, 10～50 parts alkylphenol and 5～40 parts calcium hydroxide and/or calcium oxide are mixed, carry out neutralization reaction, the acid number of described naphthenic acid is 60～180mgKOH/g, and the alkyl carbon number of described alkylphenol is 8～24;
(2) add 10～80 parts methyl alcohol and 10～50 parts calcium hydroxide and/or calcium oxide, pass into carbonic acid gas and carry out carbonation reaction, the carbonic acid gas intake is 60～140% of theoretical value;
(3) add 10～50 parts calcium hydroxide and/or calcium oxide, pass into carbonic acid gas and carry out carbonation reaction, the carbonic acid gas intake is 60～140% of theoretical value;
(4) deviate from alcohol, water, solvent and solid residue after, obtain product;
Wherein, the raw material consumption is take naphthenic acid weight as 100 parts.
Described varsol can be alkane, aromatic hydrocarbons or the mixture of the two, is preferably one or more in 60 ℃～180 ℃ straight-run spirit, benzene, toluene and dimethylbenzene of boiling range.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 kinematic viscosity (40 ℃) 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 acid number of described naphthenic acid is preferably 60～120mgKOH/g.
The weight-average molecular weight of described naphthenic acid is 250～650, is preferably 300～500.
The alkyl carbon number of described alkylphenol is preferably 10～18.In the alkylphenol, the content of the single substituted alkyl phenol of contraposition is preferred 〉=60wt%.
In the step (1), the consumption of varsol is preferably 50～300 parts; The consumption of neutral oil is preferably 50～200 parts; The consumption of water is preferably 5～40 parts.Temperature of reaction is preferably 45～60 ℃; Reaction times is preferably 30～90min.
Step also can add alkali metal hydroxide in (1), preferably adds potassium hydroxide or sodium hydroxide.Take the gross weight of water and alkali metal hydroxide as benchmark, the consumption of alkali metal hydroxide is 5%～35%, is preferably 5～20%.Alkali metal hydroxide can promote the carrying out of neutralization reaction, and makes metal detergent have better properties.
Also can add the low mass molecule alcohol of C4～C8 or their mixture in the step (2), the weight ratio of low mass molecule alcohol and methyl alcohol is 1: 0.1～1: 10.The low mass molecule alcohol class of C4～C8 is further to improve the necessary raw material of calcium naphthenate base number.
Theoretical value in step (2) and (3) is calculated and is got with calcium hydroxide and/or the calcium oxide content of each adding.
In step (2) and (3), the temperature of carbonation reaction is preferably 45～60 ℃.
Described calcium hydroxide and/or calcium oxide both can be analytical pure, also can be technical pures.
The present invention also provides the metal detergent that is made by aforesaid method.
The present invention has following useful technique effect:
(1) the present invention has effectively overcome the deficiencies in the prior art by add alkylphenol in the preparation process of calcium naphthenate, makes product of the present invention have better anti-oxidative stability, therefore has widely purposes in lubricating oil.
(2) on the basis with good anti-oxidative stability, the present invention has prepared overbased calcium naphthenate product, and its base number can reach more than the 370mgKOH/g.
Embodiment
Further specify by the following examples the present invention.
Embodiment 1
In with 500 milliliters of there-necked flasks of motor agitators and prolong, add 150 milliliters of 120# industrial napthas, 150SN neutral oil 35 grams, aqueous sodium hydroxide solution 10 grams of 10wt%, calcium hydroxide 10 grams, naphthenic acid 60 grams (acid number 85mgKOH/g), 4-dodecylphenol 14 grams (content of the single substituted alkyl phenol of contraposition is 75wt%), the control temperature of reaction is at 45～60 ℃, behind the neutralization reaction 60min, generate neutral calcium naphthenate.Add 15 gram calcium hydroxides, 20 gram methyl alcohol, 20 gram propyl carbinols, pass into carbonic acid gas, Ventilation Rate about 80ml/min, intake reach theoretical value 70% the time, add 15 gram calcium hydroxides, pass into 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, then put into medical centrifuge, 4000rpm is centrifugal with rotating speed, flash distillation thing after centrifugal is put into matrass with decompression facility, at first be warmed up to 120 ℃ of air distillations, 5 ℃/min of heat-up rate, constant temperature 30min, then carry out underpressure distillation to system, vacuum degree control is more than 0.02Mpa.Temperature is controlled at 150 ℃, and constant temperature 30min obtains at last 130 of dark thickness russet and restrains additives.Base number=the 391mgKOH/g of product, turbidity=73, product viscosity=174mm
2/ s, Ca content are 14.05%.
Embodiment 2
In with 500 milliliters of there-necked flasks of motor agitators and prolong, add 150 milliliters of 120# industrial napthas, 150SN neutral oil 35 grams, aqueous sodium hydroxide solution 10 grams of 10wt%, calcium hydroxide 10 grams, naphthenic acid 65 grams (acid number 85mgKOH/g), 4-dodecylphenol 10 grams (content of the single substituted alkyl phenol of contraposition is 75wt%), the control temperature of reaction is at 45-60 ℃, behind the neutralization reaction 60min, generate neutral calcium naphthenate.Add 15 gram calcium hydroxides, 20 gram methyl alcohol, 20 gram isopropylcarbinols, pass into carbonic acid gas, Ventilation Rate about 80ml/min, intake reach theoretical value 70% the time, add 15 gram calcium hydroxides, pass into 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, then put into medical centrifuge, 4000rpm is centrifugal with rotating speed, flash distillation thing after centrifugal is put into matrass with decompression facility, at first be warmed up to 120 ℃ of air distillations, 5 ℃/min of heat-up rate, constant temperature 30min, then carry out underpressure distillation to system, vacuum degree control is more than 0.02Mpa.Temperature is controlled at 150 ℃, and constant temperature 30min obtains at last 130 of dark thickness russet and restrains additives.Base number=the 411mgKOH/g of product, turbidity=85, product viscosity=197mm
2/ s, Ca content are 15.16%.
Embodiment 3
In with 500 milliliters of there-necked flasks of motor agitators and prolong, add 150 milliliters of 120# industrial napthas, 150SN neutral oil 35 grams, aqueous sodium hydroxide solution 10 grams of 10wt%, calcium hydroxide 10 grams, naphthenic acid 55 grams (acid number 85mgKOH/g), 4-dodecylphenol 20 grams (content of the single substituted alkyl phenol of contraposition is 75wt%), the control temperature of reaction is at 45-60 ℃, behind the neutralization reaction 60min, generate neutral calcium naphthenate.Add 15 gram calcium hydroxides, 20 gram methyl alcohol, 20 gram isopropylcarbinols, pass into carbonic acid gas, Ventilation Rate about 80ml/min, intake reach theoretical value 70% the time, add 15 gram calcium hydroxides, pass into 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, then put into medical centrifuge, 4000rpm is centrifugal with rotating speed, flash distillation thing after centrifugal is put into matrass with decompression facility, at first be warmed up to 120 ℃ of air distillations, 5 ℃/min of heat-up rate, constant temperature 30min, then carry out underpressure distillation to system, vacuum degree control is more than 0.02Mpa.Temperature is controlled at 150 ℃, and constant temperature 30min obtains at last 130 of dark thickness russet and restrains additives.Base number=the 387mgKOH/g of product, turbidity=70, product viscosity=157mm
2/ s, Ca content are 14.00%.
Comparative Examples 1
In with 500 milliliters of there-necked flasks of motor agitators and prolong, add 150 milliliters of 120# industrial napthas, 150SN neutral oil 35 grams, potassium hydroxide aqueous solution 10 grams of 10wt%, calcium hydroxide 10 grams, naphthenic acid 65 grams (acid number 85mgKOH/g), the control temperature of reaction behind the neutralization reaction 60mi n, generates neutral calcium naphthenate at 45-60 ℃.Add 15 gram calcium hydroxides, 20 gram methyl alcohol, 20 gram propyl carbinols, pass into carbonic acid gas, Ventilation Rate about 80ml/min, intake reach theoretical value 70% the time, add 15 gram calcium hydroxides, pass into 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, then put into medical centrifuge, 4000rpm is centrifugal with rotating speed, flash distillation thing after centrifugal is put into matrass with decompression facility, at first be warmed up to 120 ℃ of air distillations, 5 ℃/min of heat-up rate, constant temperature 30min, then carry out underpressure distillation to system, vacuum degree control is more than 0.02Mpa.Temperature is controlled at 150 ℃, and constant temperature 30min obtains at last 130 of dark thickness russet and restrains additives.Base number=the 385mgKOH/g of product, turbidity=91, product viscosity=184mm
2/ s, Ca content are 14.03%.
Comparative Examples 2
Adopt the method for embodiment 1, just in the carbonation reaction process, do not add propyl carbinol.Base number=the 270mgKOH/g of product, turbidity=68, product viscosity=120mm
2/ s, Ca content are 9.02%.
Embodiment 6
Highly basic calcium naphthenate product and Industrial products T114 that embodiment and Comparative Examples 1 is synthetic, call in (base oil is comprised of 500SN and 150BS) in the base oil that contains 0.5wt%T203 by the single dose of 5wt% respectively, adopt the Dupont2100 thermal analyzer to measure the most pyrolytic decomposition temperature and oxidation induction period, to investigate its anti-oxidative stability, experimental result sees Table 1.
Experiment condition is as follows:
The most pyrolytic decomposition humid test condition: oxygen gas flow rate 50ml/min oil sample 2-5mg
10 ℃/min of heat-up rate
Oxidation induction period test conditions: oxygen gas flow rate 50ml/min oil sample 1-2mg
100 ℃/min of heat-up rate
210 ℃ of steady temperatures
As can be seen from Table 1, compare with existing calcium naphthenate product, high base number calcium naphthenate product provided by the present invention has better anti-oxidative stability.
Table 1
Claims (13)
1. the preparation method of a high-base number metal detergent comprises:
(1) varsol, neutral oil, naphthenic acid, 5～40 parts water, 10～50 parts alkylphenol and 5～40 parts calcium hydroxide and/or calcium oxide are mixed, carry out neutralization reaction, the acid number of described naphthenic acid is 60～180mgKOH/g, and the alkyl carbon number of described alkylphenol is 8～24;
(2) add 10～80 parts methyl alcohol and 10～50 parts calcium hydroxide and/or calcium oxide, pass into carbonic acid gas and carry out carbonation reaction, the carbonic acid gas intake is 60～140% of theoretical value;
(3) add 10～50 parts calcium hydroxide and/or calcium oxide, pass into carbonic acid gas and carry out carbonation reaction, the carbonic acid gas intake is 60～140% of theoretical value;
(4) deviate from alcohol, water, solvent and solid residue after, obtain product;
Wherein, the raw material consumption is take naphthenic acid weight as 100 parts.
2. in accordance with the method for claim 1, it is characterized in that, the alkyl carbon number of described alkylphenol is 10～18.
3. in accordance with the method for claim 1, it is characterized in that, in the alkylphenol, the content 〉=60wt% of the single substituted alkyl phenol of contraposition.
4. in accordance with the method for claim 1, it is characterized in that, described varsol is one or more in 60 ℃～180 ℃ straight-run spirit, benzene, toluene and dimethylbenzene of boiling range.
5. in accordance with the method for claim 1, it is characterized in that, in the step (1), the consumption of varsol is 50～300 parts.
6. in accordance with the method for claim 1, it is characterized in that, described neutral oil is 100SN or 150SN.
7. in accordance with the method for claim 1, it is characterized in that, in the step (1), the consumption of neutral oil is 50～200 parts.
8. in accordance with the method for claim 1, it is characterized in that, add alkali metal hydroxide in the step (1), take the gross weight of water and alkali metal hydroxide as benchmark, the consumption of alkali metal hydroxide is 5%～35%.
9. in accordance with the method for claim 8, it is characterized in that, the consumption of alkali metal hydroxide is 5～20%.
10. in accordance with the method for claim 1, it is characterized in that, add the low mass molecule alcohol of C4～C8 or their mixture in the step (2), the weight ratio of low mass molecule alcohol and methyl alcohol is 1: 0.1～1: 10.
11. in accordance with the method for claim 1, it is characterized in that, in the step (1), temperature of reaction is 45～60 ℃; Reaction times is 30～90min.
12. in accordance with the method for claim 1, it is characterized in that, in step (2) and (3), the temperature of carbonation reaction is 45～60 ℃.
13. according to the prepared metal detergent of either method in the claim 1～12.
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| CN103725357B (en) * | 2012-10-15 | 2015-07-01 | 中国石油化工股份有限公司 | Low-alkali detergent, preparation method of detergent and lubricating oil composition containing detergent |
| CN103725355B (en) * | 2012-10-15 | 2015-07-01 | 中国石油化工股份有限公司 | Preparation method of low-base number lubricating oil clearing agent |
| CN103725353B (en) * | 2012-10-15 | 2015-07-01 | 中国石油化工股份有限公司 | Low-base number lubricating oil additive, preparation method and lubricating oil composition |
| CN103265995B (en) * | 2013-05-18 | 2014-10-29 | 黄山学院 | Preparation method of lubricating oil detergent |
| 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 |
| CN104130822B (en) * | 2014-07-03 | 2016-03-23 | 黄山学院 | A kind of terephthalic acid list lauryl alcohol ester calcium salt purification agent and synthetic method thereof |
| CN111575085A (en) * | 2020-05-27 | 2020-08-25 | 中国石油化工股份有限公司 | CF grade diesel engine oil composition, preparation method and application thereof |
| CN116478749A (en) * | 2022-01-14 | 2023-07-25 | 中国石油天然气股份有限公司 | Preparation method of ultrahigh-base-number calcium sulfonate |
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| US5314633A (en) * | 1988-06-24 | 1994-05-24 | Exxon Chemical Patents Inc. | Low pressure derived mixed phosphorous- and sulfur- containing reaction products useful in power transmitting compositions and process for preparing same |
| US5484542A (en) * | 1992-09-04 | 1996-01-16 | The Lubrizol Corporation | Sulfurized overbased compositions |
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