CN106675699A - Preparation method of ultra-overbased synthetic magnesium sulfonate - Google Patents
Preparation method of ultra-overbased synthetic magnesium sulfonate Download PDFInfo
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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
- 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
- C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
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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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Abstract
The invention provides a preparation method of ultra-overbased synthetic magnesium sulfonate. The preparation method specially comprises the following steps of adding heavy alkylbenzene sulfonate and linear alkyl benzene sulfonate into a reaction system consisting of organic solvent, micromolecule organic acid, saturated fatty acid, low carbon alcohol and the like; adding a magnesium oxide and thinning oil mixture by batches in different phases, adding an accelerant and water, introducing carbon dioxide, removing alcohol and water out of the system under certain conditions, and centrifuging under certain conditions; finally, relieving pressure and distilling, so as to obtain the ultra-overbased synthetic magnesium sulfonate. The preparation method has the advantage that the heavy alkylbenzene sulfonate and the linear alkyl benzene sulfonate are used as reaction raw materials, the magnesium oxide and thinning oil mixture is added by batches in different phases, and finally the ultra-overbased synthetic magnesium sulfonate with low settling value, low turbidity and no caking is obtained.
Description
Technical field
The present invention relates to Overbased magnesium sulphonates technical field, more particularly to a kind of Overbased magnesium sulphonates
Preparation method.
Background technology
Overbased magnesium sulphonates are sulfonate metal detergent dispersant products, and feature is that base number is high, ash content is low, neutralizes
Ability is strong, with preferable detergency and rust-preventing characteristic, is used widely in medium-to-high grade I. C. engine oil and some fuel oil.
The preparation of Overbased magnesium sulphonates is a gas, liquid, solid chemical reaction process for complexity, usually will be molten
The raw material such as agent, promotion property, base oil, magnesia, sulfonic acid or neutral ichthyodin is sequentially added in reactor, controls certain reaction
Temperature carries out neutralization reaction, and carbon dioxide is then passed through in a certain temperature conditions, carries out quaternization high, treats that alkalization high is anti-
Heat up abjection solvent and light component are carried out after should terminating, inoganic solids is then filtered to remove and other impurities is obtained the super base number of oiliness
Sulfonic acid magnesium products.As recorded a kind of overbased magnesium sulfonate technique in United States Patent (USP) 3875737 and 4148740, wherein with ammonia or
A kind of ammonium compound needs to remove the operation of ammonium salt from product and condensate liquid as accelerator in the technique；United States Patent (USP)
It is that accelerator produces overbased magnesium sulfonate to have been recorded in 4127589 using the carboxylic acid or its esters of low-molecular-weight；United States Patent (USP)
Recorded in 3629109 using substantial amounts of sulfonic acid and oil-soluble mixture of carboxylic acids and generated with water and ethanol booster response a kind of
The mixture of over base sulfosalt carboxylate；Recorded in Publication No. CN86108173 Chinese patents using one kind by butanedioic acid
A kind of method that acid anhydride produces overbased magnesium sulfonate with aphthenic acids and (or) salicylic co-accelerator, Publication No. CN1369543A
Chinese patent describe a kind of A kickers ammoniacal liquor of introducing, B accelerator (ammonium carbonate or ammonium hydrogen carbonate or urea or other two
Kind of mixture), the surfactant of carbon number 6-30 alkyl salicylates or aphthenic acids, synthesize the production of high base number magnesium alkylbenzene sulfonate
Method, Publication No. CN1067050A Chinese patents are described and use specific heavy-burned magnesia and in carbonation by water
The method that reactant mixture prepares overbased magnesium sulfonate is introduced with alcohol.
The Overbased magnesium sulphonates product base number of more than TBN400 is high, and content of magnesium is high, is often produced in carbonation
More magnesium salts waste residue, these magnesium salts waste residues Overbased magnesium sulphonates product caused by treatment is not brought into finished product thoroughly is turbid
Degree is high, and precipitation number is high, easy skinning.
The content of the invention
Present invention solves the technical problem that being to provide a kind of preparation method of Overbased magnesium sulphonates, the application system
Standby Overbased magnesium sulphonates have that turbidity is low, precipitation number it is low with not skinning the characteristics of.
In view of this, this application provides a kind of preparation method of Overbased magnesium sulphonates, comprise the following steps：
A), it is the one kind in polyisobutylene butanedioic anhydride and polyisobutene succinamide, organic solvent, small molecule is organic
Acid, saturated fatty acid, low-carbon alcohols, heavy alkylbenzene sulfonic acid mix with LINER ALKYL BENZENE SULPHONIC ACID SOFT 96, obtain mixture；
B), the mixture of magnesia and flux oil is added in the mixture, water is added after temperature reaction and is helped promotion
Agent, is passed through carbon dioxide, adds the mixture of magnesia and flux oil, is passed through carbon dioxide, the reaction that will be obtained after reaction
Material is heated to remove low-carbon (LC) alcohol and water, obtains liquid material；
Or, B), the mixture of magnesia and flux oil is added in the mixture, add water after temperature reaction and help rush
Enter agent, and be passed through carbon dioxide, then be repeated in the step of above-mentioned two adds raw material several times, to be obtained after then reacting
Reaction mass is heated to remove low-carbon (LC) alcohol and water, obtains liquid material；
C), heated after the liquid material is mixed with organic solvent, then be centrifuged, supernatant is obtained, by the supernatant
Vacuum distillation, obtains Overbased magnesium sulphonates.
Preferably, step B) in, the magnesia is 1 with the mass ratio of base oil：(1~3).
Preferably, the heavy alkylbenzene sulfonic acid and the mass ratio of the LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 are (5~35)：(35~
95)。
Preferably, the opportunity that the magnesia is added again with the dilution oil mixture is the preceding titanium dioxide being once passed through
The 60%~100% of the mole of the magnesia that carbon is once added before being.
Preferably, the active matter of the heavy alkylbenzene sulfonic acid is 65~75%, and mean molecule quantity is 420~450；It is described heavy
Alkyl benzene sulphonate is obtained by the heavy alkyl benzene that boiling range is 385 DEG C~450 DEG C with SO 3 sulfonated.
Preferably, the active matter of the LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 is 83~93%, and mean molecule quantity is 470~530；It is described
It is anti-that LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 carries out sulfonation with sulfur trioxide again by the product that toluene and the alpha-olefin of C20~C24 are alkylated
Should obtain.
Preferably, the organic solvent is dimethylbenzene, and the small molecular organic acid is formic acid, acetic acid, propionic acid or butyric acid, institute
Saturated fatty acid is stated for tetradecylic acid or stearic acid, the low-carbon alcohols are methyl alcohol, ethanol or n-butanol, the kicker is carbonic acid
The aqueous solution of hydrogen ammonium, ammoniacal liquor, ammonium carbonate, ethylenediamine or above-mentioned substance.
Preferably, step B) in, the temperature of the heating is 90~145 DEG C, and pressure is 0~-0.095mPa.
Preferably, step C) in, the liquid material is 1 with the mass ratio of the organic solvent：(0.5~3), it is described to add
The temperature of heat is 40~80 DEG C, and centrifugal force is 500~1000g.
Preferably, the quality of the magnesia is：The content of magnesia is 96~99.5%, and the content of activated magnesia is
92~95%, 40~60 DEG C of activity is 10~50S, and bulk density is 0.15~0.35g/ml.
This application provides a kind of preparation method of Overbased magnesium sulphonates, the method is first by raw material polyisobutene
One kind, organic solvent, small molecular organic acid, saturated fatty acid, low-carbon alcohols, weight in succinic anhydride and polyisobutene succinamide
Alkyl benzene sulphonate mixes with LINER ALKYL BENZENE SULPHONIC ACID SOFT 96, obtains mixture, then to addition magnesia and flux oil in the mixture
Mixture, add water and kicker and be passed through carbon dioxide, then add the mixture of magnesia and flux oil stage by stage,
Add water and kicker and be passed through carbon dioxide, reaction mass is obtained after reaction, finally carry out the purification of reaction mass, most
Overbased magnesium sulphonates are obtained eventually；In above-mentioned preparation process, the application uses heavy alkylbenzene sulfonic acid and linear alkyl benzene
Sulfonic acid ultimately facilitates carbonation reaction as reaction raw materials, and by adding the mixture of magnesia and flux oil stage by stage
During magnesia and carbon dioxide reaction fully carry out, make the small magnesium carbonate micella particle diameter to be formed, narrow range, structure steady
It is fixed, finally make that the Overbased magnesium sulphonates turbidity for obtaining is low, precipitation number it is low with not skinning.Test result indicate that, the application
The turbidity of the Overbased magnesium sulphonates of preparation is minimum up to 2.5NTU, and precipitation number places a Zhou Wujie up to 0.003%
Skin.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, but
It should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
The embodiment of the invention discloses a kind of preparation method of Overbased magnesium sulphonates, comprise the following steps：
A), it is the one kind in polyisobutylene butanedioic anhydride and polyisobutene succinamide, organic solvent, small molecule is organic
Acid, saturated fatty acid, low-carbon alcohols, heavy alkylbenzene sulfonic acid mix with LINER ALKYL BENZENE SULPHONIC ACID SOFT 96, obtain mixture；
B), the mixture of magnesia and flux oil is added in the mixture, water is added after temperature reaction and is helped promotion
Agent, and carbon dioxide is passed through, the mixture of magnesia and flux oil is added, carbon dioxide is passed through, it is anti-by what is obtained after reaction
Answer material to heat to remove low-carbon (LC) alcohol and water, obtain liquid material；
Or, B), the mixture of magnesia and flux oil is added in the mixture, add water after temperature reaction and help rush
Enter agent, and be passed through carbon dioxide, then be repeated in the step of above-mentioned two adds raw material several times, to be obtained after then reacting
Reaction mass is heated to remove low-carbon (LC) alcohol and water, obtains liquid material；
C), the liquid material that will be obtained is heated after mixing with organic solvent, then is centrifuged, and obtains supernatant, by the supernatant
Liquid vacuum distillation, obtains Overbased magnesium sulphonates.
This application provides a kind of preparation method of Overbased magnesium sulphonates, the method using heavy alkylbenzene sulfonic acid with
LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 adds the mixture of magnesia and flux oil in different phase, is passed through two by several times as reaction raw materials
Carbonoxide carries out carbonation reaction and follow-up purification process, has obtained that turbidity is low, the low superelevation alkali with not skinning of precipitation number
Value synthesis sulfonic acid magnesium.
During Overbased magnesium sulphonates are prepared, the application has carried out the mixing of raw material first, will gather different
One kind, organic solvent in butylene succinic anhydride and polyisobutene succinamide, small molecular organic acid, saturated fatty acid, low-carbon (LC)
Alcohol, heavy alkylbenzene sulfonic acid mix with LINER ALKYL BENZENE SULPHONIC ACID SOFT 96, obtain mixture.Organic solvent described in above-mentioned raw materials is this area skill
Raw material known to art personnel, has no particular limits to this application, example, and the organic solvent is preferably dimethylbenzene.Institute
State small molecular organic acid preferably formic acid, acetic acid, propionic acid or butyric acid；The saturated fatty acid is preferably tetradecylic acid or stearic acid；
The low-carbon alcohols are preferably methyl alcohol, ethanol or n-butanol.The application is to the polyisobutylene butanedioic anhydride, polyisobutene succinyl
The source of amine, organic solvent, small molecular organic acid, saturated fatty acid and low-carbon alcohols has no particular limits, be commercially available prod or
Prepared according to mode well known to those skilled in the art.The heavy alkylbenzene sulfonic acid preferably by HAB%98.5%~
100%th, the heavy alkyl benzene of 385 DEG C~450 DEG C of boiling range and sulfur trioxide gas sulfonation is obtained；The activity of the heavy alkylbenzene sulfonic acid
Thing content is 65%~75%, and mean molecule quantity is 420~450.The LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 preferably by toluene and C20~
The alpha-olefin of C24 be raw material chilli oil catalysis under be alkylated to straight chain linear alkyl benzene, the straight chain linear alkyl benzene again with three oxygen
Change sulphur gas sulfonation to obtain；The alpha-olefin of above-mentioned C20~C24 preferably include the α of the alpha-olefin of C20, the alpha-olefin of C22 and C24-
Alkene, its mass ratio is preferably (40~55)：(20~35)：(5~25).The active matter of the LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 is preferably
83~93%, mean molecule quantity is preferably 470~530.The quality of the heavy alkylbenzene sulfonic acid and the LINER ALKYL BENZENE SULPHONIC ACID SOFT 96
Than being preferably (5~35)：(35~95), more preferably (10~30)：(70~90).The reaction raw materials of the application are using weight alkyl
Benzene sulfonic acid and LINER ALKYL BENZENE SULPHONIC ACID SOFT 96, and its weight ratio is limited, be conducive to the oil soluble detergency and anti-scaling property of product.
After mixture is obtained, the application then adds the mixture of magnesia and flux oil in said mixture, tentatively
Water and co-catalyst are added after reaction, carbon dioxide is passed through, the mixture and water of magnesia and flux oil is added again and is helped
Catalyst, is passed through carbon dioxide, and low-carbon (LC) alcohol and water is removed after reaction, obtains reaction mass.In above process magnesia with it is dilute
Oil batch is released to add into reaction system, while in order that magnesia can fully react, magnesia described herein
Quality is higher, its purity up to 96%~99.5%, active oxidation content of magnesium for 92~95%, 40~60 DEG C of activity for 10~
50S, bulk density is 0.15~0.35g/ml；The activity of above-mentioned magnesia is preferably determined using citric acid neutralisation, at some
In embodiment, the activity of the magnesia is 10~35S at 50~55 DEG C.Content of magnesia described herein is high, it is active it is high,
Specific surface area is big and is difficult dispersion, can often be formed in addition reaction system and disperse bad, directly forms the coalescence of magnesia bulky grain
Group, causes oxidation magnesium utilization efficiency low, and magnesia mix with flux oil and is added to make magnesia stage by stage into stickiness
Reaction system in more readily dispersible opening do not formed coalescence group, if it is disposable add can make reaction system mobility be deteriorated and
And reaction is violent, easily forms magnesium carbonate particle buildup and be condensed into precipitation into bulky grain, cause reaction effect bad, add by several times
It is, in order to keep the mobility of system, to react more abundant.Herein described magnesia is preferably 1 with the mass ratio of flux oil：(1
~3), and magnesia is identical with the mass ratio of flux oil every time.After mixture of the magnesia with flux oil is added first, again
It is that the preceding carbon dioxide for once adding is to add the carbon dioxide being once passed through before magnesia is with the opportunity of dilution oil mixture
The 60%~100% of the mol ratio of the preceding magnesia for once adding., it is necessary to protect during magnesia and carbon dioxide is added
Card carbon dioxide is not excessive.Herein described flux oil is flux oil well known to those skilled in the art, to this without spy
Other limitation, example, the flux oil can be mineral oil, such as 150SN, 150N or artificial oil PAO.The co-catalyst
The preferably aqueous solution of ammonium hydrogen carbonate, ammoniacal liquor, ammonium carbonate, ethylenediamine or above-mentioned substance, more preferably concentration be 10wt%~
The ammoniacal liquor of 20wt%, ethylenediamine or ammonium carbonate.
According to the present invention, the mode that the magnesia is added stage by stage with flux oil can also be：In the mixture
The mixture of magnesia and flux oil is added, water and kicker are added after temperature reaction, be passed through carbon dioxide, then weigh successively
The step of multiple above-mentioned two adds raw material is several times；The mixture of magnesia and flux oil is added i.e. in the mixture, is risen
Water and kicker are added after temperature reaction, carbon dioxide is passed through, the mixture of magnesia and flux oil is added, after temperature reaction
Water and kicker are added, carbon dioxide is passed through, circulation is proceeded as described above, until oxidation reactive magnesium is complete
Entirely.The reaction that the application prepares Overbased magnesium sulphonates is specific as follows shown：
After the completion of above-mentioned reaction, the reaction mass that will be obtained is heated to remove low-carbon (LC) alcohol and water, the heating
Temperature is preferably 90~145 DEG C, and the heating is carried out under being preferably 0~-0.095mPa pressure, and the heating can remove system
Interior low-carbon alcohols, water, obtains the Overbased magnesium sulphonates semi-finished product that liquid material contains a small amount of slag, and its turbidity is relatively high,
Therefore the application needs to carry out subsequent treatment, is further ensured that the turbidity of Overbased magnesium sulphonates.The application is by the liquid
Shape material is heated after mixing with organic solvent, then is centrifuged, and obtains supernatant, the supernatant vacuum distillation is removed into solvent, then
Obtain Overbased magnesium sulphonates.In above process, the organic solvent is preferably dimethylbenzene, the liquid material with have
The mass ratio of machine solvent is preferably 1：(0.5~3), more preferably 1：(0.8~1.5)；The temperature of the heating is preferably 40~
80 weight portions, more preferably 50~70 DEG C；The centrifugal force of the centrifugation is preferably 500~1000g, more preferably 700~800g.
For a further understanding of the present invention, the Overbased magnesium sulphonates provided the present invention with reference to embodiment
Preparation method is described in detail, and protection scope of the present invention is not limited by the following examples.
The preparation of the LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 of embodiment 1
10g chilli oil and 150g toluene are added in reactor, at 50~60 DEG C to reactor in be added dropwise 100g C20~
(mass ratio of C20, C22 and C24 is 40~55 to C24 alpha-olefins：20~35：5~25), when continuing to react one section after completion of dropwise addition
Between, static 2~4h layerings take supernatant liquid filtering, then by unreacted toluene is distilled off, obtain C20~C24 long-chain linears
Alkylbenzene 120g；Sulfur trioxide gas 30g sulfonation is slowly introducing at 40~60 DEG C to C20~C24 long-chain linear alkylbenzenes again
Reaction 30 minutes, aging afterwards point of acid, obtain C20~C24 long-chain linear alkylbenzene sulfonic acid 140g (mean molecule quantity 470~
530th, 83~93wt% of activity substance content).
The preparation of heavy alkylbenzene sulfonic acid
The heavy alkyl benzene 200g that boiling range is 385 DEG C~450 DEG C is added into reactor, is delayed at 40~60 DEG C in reactor
Slowly sulfur trioxide gas 35g sulfonating reactions are passed through 30 minutes, aging afterwards point of acid obtains heavy alkylbenzene sulfonic acid 230g (active matters
Content be 65%~75%, mean molecule quantity be 420~450).
LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 in following examples is the linear alkyl benzene of the preparation of embodiment 1 with heavy alkylbenzene sulfonic acid
Sulfonic acid and heavy alkylbenzene sulfonic acid.In following examples, the content of magnesia is 96~99.5%, and the content of activated magnesia is 92
~95%, the active activity at 50~55 DEG C for using citric acid neutralisation to measure magnesia is 10~35S, and bulk density is
0.15~0.35g/ml.
Embodiment 2
To being added in the flask of 500ml, 100g dimethylbenzene, formic acid 3g, stearic acid 6g, methyl alcohol 20g, alkene acid anhydride 3g are well mixed,
Add mass ratio 10：90 heavy alkylbenzene sulfonic acid and LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 mixture 35g, it is 1 to add mass ratio：2 oxygen
Change magnesium and base oil mixture 30g, be warming up to 40~50 DEG C of neutralization 30min, add water 5g, be passed through the two of 120ml/min gas velocity
Carbonoxide 3L, adds 20% ammoniacal liquor 15g, and it is 1 to add mass ratio：2 magnesia and base oil mixture 30g, maintain temperature
It is constant, then ventilate to 13L, stop ventilation, reaction mass is heated to 100 DEG C, in removing system under -0.035mpa pressure
Alcohol water, obtain liquid material 145g, it is 120NTU to survey material turbidity；155g dimethylbenzene is added to be heated to 50 DEG C in centrifugal force
It is centrifuged under the conditions of 500g, is obtained the supernatant 297g that turbidity is 8NTU, vacuum distillation is obtained base number except removal xylene
415mgKOH/g, viscosity 120mm2The Overbased magnesium sulphonates 123g of/s, turbidity 4NTU, surveying product precipitation number is
0.002%V/V, outdoor placement one week is without skinning.
Embodiment 3
To addition 130g dimethylbenzene, acetic acid 6g, tetradecylic acid 3g, methyl alcohol 10g, polyisobutene succinyl in the flask of 500ml
Amine 4g is well mixed, and it is 20 to add mass ratio：80 heavy alkylbenzene sulfonic acid and LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 mixture 30g, add matter
Amount is than being 1：2 magnesia and base oil mixture 35g, are warming up to 55~60 DEG C of neutralization 30min, add 20% ethylenediamine water-soluble
Liquid 15g, is passed through the carbon dioxide 5L of 60ml/min gas velocity, adds 20% ethylenediamine solution 15g, and it is 1 to add mass ratio：2
Magnesia and base oil mixture 35g, remain temperature-resistant, then ventilate to 15L, stop ventilation, in -0.06mpa pressure
Lower that reaction mass is heated to 90 DEG C, the alcohol water in removing system obtains liquid material 165g, and it is 100NTU to survey material turbidity,
Add 135g dimethylbenzene to be heated to 70 DEG C to be centrifuged under the conditions of centrifugal force 700g, obtain the supernatant that turbidity is 10NTU
295g, vacuum distillation obtains base number 445mgKOH/g, viscosity 180mm except removal xylene2The overbased synthesis of/s, turbidity 5NTU
Sulfonic acid magnesium 132g, it is 0.004% to survey product precipitation number, outdoor to place one week without skinning.
Embodiment 4
To addition 150g dimethylbenzene, formic acid 5g, tetradecylic acid 2g, n-butanol 15g, polyisobutene fourth two in the flask of 500ml
Acid amides 3g is well mixed, and it is 30 to add mass ratio：70 heavy alkylbenzene sulfonic acid and LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 mixture 45g, add
Mass ratio is 1：1.5 magnesia and base oil mixture 25g, are warming up to 50~55 DEG C of neutralization 30min, add 10% ammonium carbonate
Aqueous solution 15g, is passed through the carbon dioxide 6L of 80ml/min gas velocity, and it is 1 to add water 15g, add mass ratio：1.5 magnesia
With base oil mixture 25g, remain temperature-resistant, then ventilate to 12L, stop ventilation, reaction under -0.08mpa pressure
Material is heated to 100 DEG C, the alcohol water in removing system, obtains liquid material 135g, and it is 50NTU to survey material turbidity, adds 165g
Dimethylbenzene is heated to 70 DEG C and is centrifuged under the conditions of centrifugal force 800g, obtains the supernatant 297g that turbidity is 6NTU, and decompression is steamed
Distillation removal xylene obtains base number 425mgKOH/g, viscosity 160mm2/ s, the Overbased magnesium sulphonates of turbidity 2.5NTU
123g, it is 0.003%V/V to survey product precipitation number, and outdoor placement one week is without skinning.
Comparative example 1
To being added in the flask of 500ml, 100g dimethylbenzene, formic acid 3g, stearic acid 6g, methyl alcohol 20g, alkene acid anhydride 3g are well mixed,
Heavy alkylbenzene sulfonic acid 35g is added, magnesia 10g, base oil 40g is added, 40~50 DEG C of neutralization 30min are warming up to, water 5g is added,
The carbon dioxide 3L of 120ml/min gas velocity is passed through, 20% ammoniacal liquor 15g is added, is added magnesia 10g, remain temperature-resistant, connect
Ventilation to 13L, stops ventilation, reaction mass is heated to 100 DEG C under -0.035mpa pressure, the alcohol water in removing system,
Liquid muddiness material 145g is obtained, is added 155g dimethylbenzene to be heated to 50 DEG C and is centrifuged under the conditions of centrifugal force 500g, obtained
Turbidity is the supernatant 210g of 500NTU, and vacuum distillation obtains base number 370mgKOH/g, viscosity 270mm except removal xylene2/ s is turbid
The Overbased magnesium sulphonates 87g of 200NTU is spent, it is 0.4%V/V, 12 hours skinning of outdoor placement to survey product precipitation number.
Comparative example 2
To addition 130g dimethylbenzene, acetic acid 6g, tetradecylic acid 3g, methyl alcohol 10g, polyisobutene succinyl in the flask of 500ml
Amine 3g is well mixed, LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 30g, adds base oil 40, magnesia 12g to be warming up to 55~60 DEG C of neutralizations
30min, adds 20% ethylenediamine solution 15g to be passed through the carbon dioxide 5L of 60ml/min gas velocity, adds 20% ethylenediamine water-soluble
Liquid 15g, magnesia 12g is added, remain temperature-resistant, then ventilated to 15L, stop ventilation, the handle under -0.06mpa pressure
Reaction mass is heated to 90 DEG C, the alcohol water in removing system, obtains liquid muddiness material 160g, adds 135g dimethylbenzene to be heated to
70 DEG C are centrifuged under the conditions of centrifugal force 700g, obtain the supernatant 230g that turbidity is 460NTU, and vacuum distillation removes diformazan
Benzene obtains base number 385mgKOH/g, viscosity 170mm2The Overbased magnesium sulphonates 82g of/s, turbidity 189NTU, surveys product and sinks
Shallow lake value is 0.6%, and outdoor placement skinning occurs after one day.
The explanation of above example is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that right
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or uses the present invention.
Various modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The scope most wide for causing.
Claims (10)
1. a kind of preparation method of Overbased magnesium sulphonates, comprises the following steps：
A), by one kind in polyisobutylene butanedioic anhydride and polyisobutene succinamide, organic solvent, small molecular organic acid, full
Mix with LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 with aliphatic acid, low-carbon alcohols, heavy alkylbenzene sulfonic acid, obtain mixture；
B), the mixture of magnesia and flux oil is added in the mixture, water and kicker is added after temperature reaction, led to
Enter carbon dioxide, add the mixture of magnesia and flux oil, be passed through carbon dioxide, the reaction mass that will be obtained after reaction adds
Heat obtains liquid material to remove low-carbon (LC) alcohol and water；
Or, B), the mixture of magnesia and flux oil is added in the mixture, add water after temperature reaction and help promotion
Agent, and carbon dioxide is passed through, then be repeated in the step of above-mentioned two adds raw material several times, it is anti-by what is obtained after then reacting
Answer material to heat to remove low-carbon (LC) alcohol and water, obtain liquid material；
C), heated after the liquid material is mixed with organic solvent, then be centrifuged, obtain supernatant, by supernatant decompression
Distillation, obtains Overbased magnesium sulphonates.
2. preparation method according to claim 1, it is characterised in that step B) in, the matter of the magnesia and base oil
Amount is than being 1：(1~3).
3. preparation method according to claim 1, it is characterised in that the heavy alkylbenzene sulfonic acid and the linear alkyl benzene
The mass ratio of sulfonic acid is (5~35)：(35~95).
4. preparation method according to claim 1, it is characterised in that the magnesia is with the dilution oil mixture again
The opportunity of addition is the 60%~100% of the mole of the magnesia once added before the preceding carbon dioxide being once passed through is.
5. preparation method according to claim 1, it is characterised in that the active matter of the heavy alkylbenzene sulfonic acid is 65~
75%, mean molecule quantity is 420~450；The heavy alkylbenzene sulfonic acid is by heavy alkyl benzene and three that boiling range is 385 DEG C~450 DEG C
Oxidation is sulphur vulcanization to be obtained.
6. preparation method according to claim 1, it is characterised in that the active matter of the LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 is 83~
93%, mean molecule quantity is 470~530；The LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 carries out alkyl by the alpha-olefin of toluene and C20~C24
The product of change carries out sulfonating reaction and obtains with sulfur trioxide again.
7. preparation method according to claim 1, it is characterised in that the organic solvent is dimethylbenzene, the small molecule
Organic acid be formic acid, acetic acid, propionic acid or butyric acid, the saturated fatty acid be tetradecylic acid or stearic acid, the low-carbon alcohols be methyl alcohol,
Ethanol or n-butanol, the kicker are the aqueous solution of ammonium hydrogen carbonate, ammoniacal liquor, ammonium carbonate, ethylenediamine or above-mentioned substance.
8. preparation method according to claim 1, it is characterised in that step B) in, the temperature of the heating is 90~145
DEG C, pressure is 0~-0.095mPa.
9. preparation method according to claim 1, it is characterised in that step C) in, the liquid material is organic with described
The mass ratio of solvent is 1：(0.5~3), the temperature of the heating is 40~80 DEG C, and centrifugal force is 500~1000g.
10. preparation method according to claim 1, it is characterised in that the quality of the magnesia is：The content of magnesia
It is 96~99.5%, the content of activated magnesia is 10~50S for 92~95%, 40~60 DEG C of activity, and bulk density is
0.15~0.35g/ml.
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| CN108531249A (en) * | 2018-03-23 | 2018-09-14 | 新乡市瑞丰新材料股份有限公司 | A kind of preparation method of high content of magnesium magnesium alkylbenzene sulfonate |
| CN113186015A (en) * | 2021-02-02 | 2021-07-30 | 安徽澳润新材料有限公司 | High-base-number magnesium sulfonate detergent and preparation method thereof |
| CN113234517A (en) * | 2021-05-07 | 2021-08-10 | 新乡市瑞丰新材料股份有限公司 | Preparation method of nano-grade high-boron-content composite magnesium detergent |
| CN113322109A (en) * | 2021-06-11 | 2021-08-31 | 新乡市瑞丰新材料股份有限公司 | Vanadium inhibitor composition with high magnesium content and preparation method thereof |
| 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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| CN108531249A (en) * | 2018-03-23 | 2018-09-14 | 新乡市瑞丰新材料股份有限公司 | A kind of preparation method of high content of magnesium magnesium alkylbenzene sulfonate |
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| CN113234517A (en) * | 2021-05-07 | 2021-08-10 | 新乡市瑞丰新材料股份有限公司 | Preparation method of nano-grade high-boron-content composite magnesium detergent |
| CN113322109A (en) * | 2021-06-11 | 2021-08-31 | 新乡市瑞丰新材料股份有限公司 | Vanadium inhibitor composition with high magnesium content and preparation method thereof |
| 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 |
| CN113549481B (en) * | 2021-07-29 | 2023-03-31 | 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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