CN104276945B - A kind of preparation method of boronation overbased calcium alkyl-salicylate - Google Patents
A kind of preparation method of boronation overbased calcium alkyl-salicylate Download PDFInfo
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- CN104276945B CN104276945B CN201310274062.7A CN201310274062A CN104276945B CN 104276945 B CN104276945 B CN 104276945B CN 201310274062 A CN201310274062 A CN 201310274062A CN 104276945 B CN104276945 B CN 104276945B
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- salicylate
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- overbased calcium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- 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
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/26—Carboxylic acids; Salts thereof
- C10M129/56—Acids of unknown or incompletely defined constitution
- C10M129/58—Naphthenic acids
-
- 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
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
-
- 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
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/16—Naphthenic acids
-
- 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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
-
- 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
- C10N2030/04—Detergent property or dispersant property
-
- 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
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
-
- 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
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
Abstract
The invention discloses a kind of preparation method of boronation overbased calcium alkyl-salicylate.The present invention's sherwood oil replaces neutralization and carbonation reaction to commonly use varsol at present as toluene, dimethylbenzene, industrial naptha etc., can avoid changing reaction solvent when next step boration reacts, temperature of reaction is too high, carbonic acid gas spilling is too fast, degradation problem under product base number.Meanwhile, final stage reclaim petroleum ether solvent, also can avoid boronation overbased calcium alkyl-salicylate complicated process of preparation and aftertreatment loaded down with trivial details, relatively save production cost, reduce energy consumption.In addition, boronation overbased calcium alkyl-salicylate not only can play purification agent effect, and boratory existence simultaneously can promote oxidation stability and the rustless property of purification agent further.
Description
Technical field
The present invention relates to a kind of preparation method of boronation overbased calcium alkyl-salicylate.
Background technology
Overbased calcium alkyl-salicylate detergent for lubricating oil is a class salient features improving agent of marine cylinder oil first-selection, it is on the one hand as tensio-active agent, by its solubilising, peptization or peace and quiet dissemination, suppress the severe contamination harm that fuel and lubricating oil in marine diesel cause, alkalescence can also be provided to stock on the other hand, the harmful mineral acid inevitably generated under actual applying working condition with fuel and lubricating oil effectively and organic acid, thus reach and slow down oil oxidation and decay, reduce marine diesel corrosive wear, extend the object in oil product and marine diesel work-ing life.
Patent about the preparation of overbased calcium alkyl-salicylate is very many, as US4100084, US2938828, US2865956, CN102071085A, CN101885677A, CN1465560A etc., its preparation method is generally: take naphthenic acid as raw material, add neutral oil and varsol, employing low mass molecule alcohol is promotor, pass into carbonic acid gas and carry out carbonation reaction, reaction terminates rear intensification dealcoholysis dehydration, obtains overbased calcium alkyl-salicylate (TBN > 300) through aftertreatment.But the colloidal particle of above-mentioned overbased calcium alkyl-salicylate mainly exists with calcium carbonate form, and the mistake basicity metal detergent of this carbonating can accelerate the oxidation of oil product under harsh operational conditions, causes metal parts to wear and tear.In recent years, foreign study staff development and to have developed with borate be the boride metal purification agent of colloidal particle.Boride metal purification agent not only has the effect of purification agent, and has good oxidation stability, friction resistant wearing and tearing, the performance such as antirust, one of focus becoming research and development.
US3480548 describe solvent-free under, a kind of high-base-number detergent is reacted with boric acid and other borating agent and is generated boride metal purification agent at 150 ~ 175 DEG C.This method temperature is higher, simultaneously at solvent-free lower easy generation foam.
US3679584 describes boration and carbonation reaction one step is carried out simultaneously, and advantage is that the borate generated is conducive to the lifting of oxidation stability and rustless property, and shortcoming is that the borated detergents base number generated is not high.
US3829381 describes one and first synthesizes high-base-number detergent, and then similar US3480548 boration reaction conditions prepares the method for borated detergents.
US4683126 describes in protic and hydrocarbon polymer mixed solvent, boron acidizing reagent joined in high-base number metal detergent, stirs, filter, slough mixed solvent after obtain a kind of purification agent of boronation.
The technology of preparing of boronation overbased calcium alkyl-salicylate there is no patent report, and simultaneously existing borated detergents technology of preparing exists that boration temperature is too high, boration uses the complicated and not high problems of borated detergents base number of solvent.
Summary of the invention
The object of this invention is to provide a kind of preparation method of boronation overbased calcium alkyl-salicylate, this preparation method's temperature of reaction is low, the reaction times is short, solvent utilization ratio is high and the boronation naphthenic acid purification agent base number of preparation is high.
Technical scheme of the present invention is:
A preparation method for boronation overbased calcium alkyl-salicylate, is characterized in that the concrete steps of the method are:
A, be sherwood oil 130-150 part of 90 ~ 120 DEG C by parts by weight boiling range, MVI150 neutral oil 30-50 part, naphthenic acid 50-70 part, methyl alcohol 15-20 part, a kind of 2-5 part in ammoniacal liquor, ammonium chloride, bicarbonate of ammonia, isopropylcarbinol 3-5 part, water 2-4 part and calcium hydroxide 60-80 part join in reactor, control temperature of reaction at 50 ~ 60 DEG C, carry out neutralization reaction 1 ~ 2h, generate neutral calcium naphthenate;
B, pass into carbonic acid gas carry out carbonation reaction 3 ~ 6h at 45 ~ 55 DEG C, carbonic acid gas intake is 60% ~ 70% of theoretical value;
Alcohol, water are sloughed in C, intensification, and the sherwood oil then adding 70-90 part boiling range 90 ~ 120 DEG C carries out centrifugal or removes residue with filter aid, and wherein flocculating aids is selected from diatomite;
D, the boric acid adding 10-15 part carry out boration reaction 5-10h, and then the sherwood oil of underpressure distillation removing boiling range 90 ~ 120 DEG C obtains product.
Naphthenic acid described in steps A of the present invention is macromole petroleum acid, and its acid number is 90 ~ 110mgKOH/g, and molecular weight is 350 ~ 650.
In step B of the present invention, carbonic acid gas air flow is 40 ~ 80ml/min.
In step C of the present invention, centrifugation rate is 3500 ~ 4500r/min.
Advantage of the present invention is: replace neutralization and carbonation reaction to commonly use varsol at present as toluene, dimethylbenzene, industrial naptha etc. with sherwood oil (boiling range 90 ~ 120 DEG C), can avoid changing reaction solvent when next step boration reacts, temperature of reaction is too high, carbonic acid gas spilling is too fast, degradation problem under product base number.Meanwhile, final stage reclaim sherwood oil (boiling range 90 ~ 120 DEG C) solvent, also can avoid boronation overbased calcium alkyl-salicylate complicated process of preparation and aftertreatment loaded down with trivial details, relatively save production cost, reduce energy consumption.In addition, boronation overbased calcium alkyl-salicylate not only can play purification agent effect, and boratory existence simultaneously can promote oxidation stability and the rustless property of purification agent further.
Embodiment
Embodiment 1:
Sherwood oil (boiling range 90 ~ 120 DEG C) 140g is added in the there-necked flask stirred and reflux, MVI150 neutral oil 40g, naphthenic acid 60g(acid number 95mgKOH/g), methyl alcohol 17g, ammoniacal liquor 3g, isopropylcarbinol 4g, water 3g, calcium hydroxide 70g, control temperature of reaction at 50 ~ 60 DEG C, after neutralization reaction 60min, generate neutral calcium naphthenate.Then CO is passed into
2, Ventilation Rate is 60ml/min, and when air flow reaches 70% of theoretical air flow, reaction terminates.After carbonation reaction terminates, be warming up to 120 DEG C and slough alcohol and water.80g sherwood oil (boiling range 90 ~ 120 DEG C) added by the material obtained, and then putting into whizzer, is that 4000r/min is centrifugal with centrifugation rate.Being poured into by clear liquid after centrifugal is equipped with in the flask of water trap, add 12g boric acid, first 120 DEG C of reflux water-dividings are warming up to, after reaction 6h water trap taken off and change reliever into underpressure distillation is carried out to system, vacuum degree control is more than-0.05MPa, and constant temperature obtains product in 30 minutes after solvent all steams.Product is reddish-brown transparent liquid, base number TBN=320mgKOH/g.
Embodiment 2:
Sherwood oil (boiling range 90 ~ 120 DEG C) 150g is added in the there-necked flask stirred and reflux, MVI150 neutral oil 45g, naphthenic acid 65g(acid number 95mgKOH/g), methyl alcohol 18g, bicarbonate of ammonia 3g, isopropylcarbinol 4g, water 3g, calcium hydroxide 70g, control temperature of reaction at 50 ~ 60 DEG C, after neutralization reaction 60min, generate neutral calcium naphthenate.Then CO is passed into
2, Ventilation Rate is 40ml/min, and when air flow reaches 70% of theoretical air flow, reaction terminates.After carbonation reaction terminates, be warming up to 120 DEG C and slough alcohol and water.80g sherwood oil (boiling range 90 ~ 120 DEG C) added by the material obtained, and then putting into whizzer, is that 4500r/min is centrifugal with centrifugation rate.Being poured into by clear liquid after centrifugal is equipped with in the flask of water trap, add 13g boric acid, first 120 DEG C of reflux water-dividings are warming up to, after reaction 8h water trap taken off and change reliever into underpressure distillation is carried out to system, vacuum degree control is more than-0.05MPa, and constant temperature obtains product in 30 minutes after solvent all steams.Product is reddish-brown transparent liquid, base number TBN=333mgKOH/g.
Embodiment 3:
Sherwood oil (boiling range 90 ~ 120 DEG C) 140g is added in the there-necked flask stirred and reflux, MVI150 neutral oil 35g, naphthenic acid 60g(acid number 95mgKOH/g), methyl alcohol 17g, ammonium chloride 5g, isopropylcarbinol 4g, water 3g, calcium hydroxide 70g, control temperature of reaction at 50 ~ 60 DEG C, after neutralization reaction 60min, generate neutral calcium naphthenate.Then CO is passed into
2, Ventilation Rate is 40ml/min, and when air flow reaches 70% of theoretical air flow, reaction terminates.After carbonation reaction terminates, be warming up to 120 DEG C and slough alcohol and water.80g sherwood oil (boiling range 90 ~ 120 DEG C) added by the material obtained, and then putting into whizzer, is that 4500r/min is centrifugal with centrifugation rate.Being poured into by clear liquid after centrifugal is equipped with in the flask of water trap, add 13g boric acid, first 120 DEG C of reflux water-dividings are warming up to, after reaction 8h water trap taken off and change reliever into underpressure distillation is carried out to system, vacuum degree control is more than-0.05MPa, and constant temperature obtains product in 30 minutes after solvent all steams.Product is reddish-brown transparent liquid, base number TBN=331mgKOH/g.
Embodiment 4: add sherwood oil (boiling range 90 ~ 120 DEG C) 140g in the there-necked flask stirred and reflux, MVI150 neutral oil 40g, naphthenic acid 60g(acid number 95mgKOH/g), methyl alcohol 17g, ammoniacal liquor 3g, isopropylcarbinol 4g, water 3g, calcium hydroxide 75g, control temperature of reaction at 50 ~ 60 DEG C, after neutralization reaction 60min, generate neutral calcium naphthenate.Then CO is passed into
2, Ventilation Rate is 55ml/min, and when air flow reaches 70% of theoretical air flow, reaction terminates.After carbonation reaction terminates, be warming up to 120 DEG C and slough alcohol and water.75g sherwood oil (boiling range 90 ~ 120 DEG C) added by the material obtained, and then adds in 15g super-cell, removed by residue with decompression vacuum pumping filter flask.Being poured into by clear liquid after filtration is equipped with in the flask of water trap, add 12g boric acid, first 120 DEG C of reflux water-dividings are warming up to, after reaction 6h water trap taken off and change reliever into underpressure distillation is carried out to system, vacuum degree control is more than-0.05MPa, and constant temperature obtains product in 30 minutes after solvent all steams.Product is reddish-brown transparent liquid, base number TBN=322mgKOH/g.
Embodiment 5:
Sherwood oil (boiling range 90 ~ 120 DEG C) 140g is added in the there-necked flask stirred and reflux, MVI150 neutral oil 40g, naphthenic acid 60g(acid number 95mgKOH/g), methyl alcohol 17g, bicarbonate of ammonia 3g, isopropylcarbinol 4g, water 5g, calcium hydroxide 66g, control temperature of reaction at 50 ~ 60 DEG C, after neutralization reaction 100min, generate neutral calcium naphthenate.Then CO is passed into
2, Ventilation Rate is 60ml/min, and when air flow reaches 70% of theoretical air flow, reaction terminates.After carbonation reaction terminates, be warming up to 120 DEG C and slough alcohol and water.80g sherwood oil (boiling range 90 ~ 120 DEG C) added by the material obtained, and then adds in 15g super-cell, removed by residue with decompression vacuum pumping filter flask.Being poured into by clear liquid after filtration is equipped with in the flask of water trap, add 12g boric acid, first 120 DEG C of reflux water-dividings are warming up to, after reaction 6h water trap taken off and change reliever into underpressure distillation is carried out to system, vacuum degree control is more than-0.05MPa, and constant temperature obtains product in 30 minutes after solvent all steams.Product is reddish-brown transparent liquid, base number TBN=310mgKOH/g.
Embodiment 6:
Sherwood oil (boiling range 90 ~ 120 DEG C) 140g is added in the there-necked flask stirred and reflux, MVI150 neutral oil 40g, naphthenic acid 66g(acid number 95mgKOH/g), methyl alcohol 17g, ammonium chloride 3g, isopropylcarbinol 4g, water 3g, calcium hydroxide 70g, control temperature of reaction at 50 ~ 60 DEG C, after neutralization reaction 60min, generate neutral calcium naphthenate.Then CO is passed into
2, Ventilation Rate is 60ml/min, and when air flow reaches 70% of theoretical air flow, reaction terminates.After carbonation reaction terminates, be warming up to 120 DEG C and slough alcohol and water.80g sherwood oil (boiling range 90 ~ 120 DEG C) added by the material obtained, and then adds in 15g super-cell, removed by residue with decompression vacuum pumping filter flask.Being poured into by clear liquid after filtration is equipped with in the flask of water trap, add 12g boric acid, first 120 DEG C of reflux water-dividings are warming up to, after reaction 6h water trap taken off and change reliever into underpressure distillation is carried out to system, vacuum degree control is more than-0.05MPa, and constant temperature obtains product in 30 minutes after solvent all steams.Product is reddish-brown transparent liquid, base number TBN=306mgKOH/g.
Claims (2)
1. a preparation method for boronation overbased calcium alkyl-salicylate, is characterized in that the concrete steps of the method are:
A, be sherwood oil 130-150 part of 90 ~ 120 DEG C by parts by weight boiling range, MVI150 neutral oil 30-50 part, naphthenic acid 50-70 part, methyl alcohol 15-20 part, a kind of 2-5 part in ammoniacal liquor, ammonium chloride, bicarbonate of ammonia, isopropylcarbinol 3-5 part, water 2-4 part and calcium hydroxide 60-80 part join in reactor, control temperature of reaction at 50 ~ 60 DEG C, carry out neutralization reaction 1 ~ 2h, generate neutral calcium naphthenate; Described naphthenic acid is macromole petroleum acid, and its acid number is 90 ~ 110mgKOH/g, and molecular weight is 350 ~ 650;
B, pass into carbonic acid gas carry out carbonation reaction 3 ~ 6h at 45 ~ 55 DEG C, carbonic acid gas intake is 60% ~ 70% of theoretical value; Carbonic acid gas air flow is 40 ~ 80ml/min;
Alcohol, water are sloughed in C, intensification, and the sherwood oil then adding 70-90 part boiling range 90 ~ 120 DEG C carries out centrifugal or removes residue with filter aid, and wherein flocculating aids is selected from diatomite;
D, the boric acid adding 10-15 part carry out boration reaction 5-10h, and then the sherwood oil of underpressure distillation removing boiling range 90 ~ 120 DEG C obtains product.
2. the method for claim 1, is characterized in that in step C, centrifugation rate is 3500 ~ 4500r/min.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4683126A (en) * | 1985-03-08 | 1987-07-28 | Nippon Oil Co., Ltd. | Method for producing alkaline earth metal borate dispersions |
| CN1465560A (en) * | 2002-06-28 | 2004-01-07 | 中国石油天然气股份有限公司 | Process for preparing ultrahigh basicity calcium naphthenate |
| 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 |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4683126A (en) * | 1985-03-08 | 1987-07-28 | Nippon Oil Co., Ltd. | Method for producing alkaline earth metal borate dispersions |
| CN1465560A (en) * | 2002-06-28 | 2004-01-07 | 中国石油天然气股份有限公司 | Process for preparing ultrahigh basicity calcium naphthenate |
| 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 |
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