CN102295971A - High base number calcium heavy alkyl benzene sulfonate detergent and preparation method thereof - Google Patents
High base number calcium heavy alkyl benzene sulfonate detergent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high base number calcium heavy alkyl benzene sulfonate detergent and a preparation method thereof. The detergent comprises 80 to 160 parts by weight of vaterite type calcium carbonate, 78 to 89 parts by weight of calcium heavy alkyl benzene sulfonate and 40 to 90 parts by weight of base oil, and the particle size of particles in the detergent is 10 to 60 nm. The preparation method comprises the follow steps: preparing a solution of calcium heavy alkyl benzene sulfonate, adding an alcohol promoter, an activating accelerator, alkaline earth metal halides and mixed alkaline calcium salt, allowing carbon dioxide to enter into obtained mixture for an alkalization reaction so as to obtain a crude product, diluting the crude product with base oil and removing solid residues and nonpolar solvents, the alcohol promoter, the activating accelerator and water to obtain the target product. The high base number calcium heavy alkyl benzene sulfonate detergent provided in the invention has high content of alkali and low viscosity, and is clear and stable.
Description
Technical field
The present invention relates to a kind of high base number heavy alkyl benzene calcium sulfonate purification agent and preparation method thereof.
Background technology
Metal detergent is one of topmost additive in the internal combustion (IC) engine lubricating oil such as automobile, boats and ships.Its role is to: suppress and remove the high temperature deposition thing of piston face, reduce the mechanical surface wearing and tearing; In and the acidic substance that produced of fuel oil incomplete combustion and oil product high temperature oxidation, prevent the device corrosion, significantly prolong oil product and engine purpose in work-ing life thereby reach.Such purification agent is usually by tensio-active agent (for example, sulfonate, alkylsalicylate and sulfuration alkyl salt etc.), carbonate (or borate) and the compound composition of thinning oil (for example, synthetic oil or mineral oil).Wherein, tensio-active agent is a dispersion agent, with micelle form stable dispersion carbonate (or borate) particle, and the paint film, colloid and the carbon distribution that exist in the solubilising cylinder; Carbonate (or borate) is neutralizing agent, in providing and the necessary alkali of acidic by-products; Thinning oil then as load micelle, micellar Oil solvent, plays dispersion medium.
Industrial extensive employing total basicnumber (TBN) is estimated the alkali content of purification agent product, is unit with Equivalent Hydrogen potassium oxide milligram number (mg KOH/g), and adopts standards such as ASTM D2896, GB/T0251 to measure.Generally speaking, the product that alkali content is higher than 300mg KOH/g is called the high base number purification agent.
Calcium sulfonate with high base number class purification agent wherein, because its raw material is easy to get, metallization process is simple and have excellent detergency, rust-preventing characteristic and thermostability concurrently, through the development of decades, become in the internal combustion (IC) engine lubricating oil be most widely used, one of the metal detergent of output maximum.The calcium sulfonate with high base number purification agent not only can be used to allocate have various properties cylinder oil (for example, the ZL96105367.4 lubricating oil composition, CN1524936A ship use intermediate speed tubular diesel engine oil, ZL200410013726.5 energy-conserving and environment-protective lubricating oil, ZL200610042979.4 Sweet natural gas and gasoline dual purpose fuel engine lubricating oil) and additive is (for example, CN1293230A fuel oil additive of controlling motor vehicle exhaust, CN1320682A oil dope, CN101100624A lubricated oil additives and preparation method thereof), further modification is converted into and has extreme-pressure anti-wear, high-low temperature resistant, the complex calcium sulfonate grease of high machinery and colloid stability (for example, ZL02130820.9 high base number composite calcium sulfonate lubricating grease and preparation method thereof, ZL200310113489.5 complex lithium grease and preparation method thereof, ZL200510073101.2 composite calcium sulfonate grease lubricant and preparation method thereof).Therefore, how efficientlying preparation calcium sulfonate with high base number purification agent has been subjected to paying close attention to widely.
The preparation technology of calcium sulfonate with high base number purification agent mainly contains following two kinds: one-step synthesis process and multistep processes synthesis technique.One-step synthesis process is the method that carbonating of employing obtains the high base number purification agent; The purification agent product of low alkali value continued to add material again and improves the method that alkali content makes the high base number purification agent by follow-up carbonating during the multistep processes synthesis technique then obtained by preliminary carbonating earlier.As far back as nineteen sixty U.S. Pat 2937991 disclose the method for using sulfonate stable dispersion lime carbonate in non-polar solvent.In subsequently more than 30 year, external scientists is by optimizing ingredient proportion, technical process, preferred feedstock and promotor, the patent that discloses multiple calcium sulfonate with high base number purification agent and preparation method thereof in succession is (as US4810396, US4929373, US4995993, US5011618 etc.).By comparison, domestic correlative study is started late, the patent disclosure that the preparation and the application of Sulfonates purification agent are just arranged up to eighties of last century the nineties successively: the method that has occurred using mixed surfactant to prepare sulfonate with high base number calcium salt purification agent (for example, low turbidity high base number mahogany acid calcium additive of ZL03104813.7 and preparation method thereof, the ZL97195134.9 overbased metal-containing detergents); Proposed to adopt high-gravity rotating bed technology to substitute the method (preparation method of ZL200410037885.9 calcium sulfonate with high base number detergent for lubricating oil, CN101451087B method for preparing lubricant oil metal detergent) that traditional mechanical stirring kettle formula preparation method obtains the narrow distribution calcium sulfonate detergents of particle diameter.
It is as follows that typical calcium sulfonate detergents prepares scheme: at first, use the calcium oxide p-sulfonic acid to neutralize, obtain calcium sulphonate; Then, under the situation of calcium sulphonate and the existence of other auxiliary material, alkaline calcium salt is carried out carbonating, the lime carbonate of generation is stably laid in product under the parcel of tensio-active agent, thereby obtained the calcium sulfonate with high base number purification agent with carbonic acid gas.
But, at present the calcium carbonate granule in the related and industrialized calcium sulfonate detergents product all is to have (Journal of Colloid and Interface Science with unformed shape in the invention disclosed patent, 1991,144:324-339).Because the more unformed carbonic acid calcium of crystal form lime carbonate has better extreme pressure, wear resisting property (Tribology Letters, 2004,17:715-721; 2008,29:33-44).But usually under higher carbonating degree, unformed carbonic acid calcium can be converted into calcite crystallization macrobead precipitation and separate out, and destroys the base number deposit of product, can not get purification agent product (the Journal of Colloid and InterfaceScience of crystal type, 1991,144:324-339).
Summary of the invention
The purpose of this invention is to provide a kind of high base number heavy alkyl benzene calcium sulfonate purification agent and preparation method thereof, this purification agent alkali content height, viscosity is low, clarification is stable, and lime carbonate exists with the vaterite-type crystallized form.
Technical scheme of the present invention is: a kind of high base number heavy alkyl benzene calcium sulfonate purification agent, be made up of the vaterite-type calcium carbonate of 80～160 mass parts, the heavy alkyl benzene calcium sulfonate of 78～89 mass parts and the base oil of 40～90 mass parts, particle grain size is 10～60nm in this purification agent.
Described base oil is preferably I class, II class or the III class base oil in the API classification, more preferably 100SN, 150SN, 200SN or 350SN base oil.
The preparation method of described high base number heavy alkyl benzene calcium sulfonate purification agent may further comprise the steps successively:
(1) preparation of heavy alkyl benzene calcium sulfonate solution: the heavy alkylbenzene sulfonic acid of 100 mass parts is dissolved in the non-polar solvent of 200～380 mass parts, under 30～50 ℃ of temperature, add the low-carbon alcohol promotor of 10～30 mass parts and the calcium oxide of 8～12 mass parts, and stirring reaction;
(2) high base number heavy alkyl benzene calcium sulfonate purification agent is synthetic: add the low-carbon alcohol promotor of 5～35 mass parts, the secondary accelerator of 0～1.5 mass parts, the alkaline earth metal halide of 0.5～4.5 mass parts and the mixed-alkali calcium salt of 50～90 mass parts in above-mentioned heavy alkyl benzene calcium sulfonate solution, mix, controlled temperature is 30～60 ℃, in system, feed carbonic acid gas and carried out quaternization, obtain thick product; Described mixed-alkali calcium salt is the mixture that calcium oxide and calcium hydroxide are formed, and the mass ratio of calcium oxide and calcium hydroxide is 1: 7～4.5: 1;
Wherein, adding total amount in one of step (1) and step (2) at least is the base oil of 40～90 mass parts: base oil added before low-carbon alcohol promotor and calcium oxide in the step (1), and was that base oil is added in the thick product in the step (2);
(3) aftertreatment: at first separate the solid residue of removing in the thick product, non-polar solvent, low-carbon alcohol promotor, secondary accelerator and water are removed in distillation then, can obtain target product.
If add base oil in step (1), the preparation system enlarges, and helps relaxing the strong heat release of neutralization reaction, and reaction control is convenient in the temperature fluctuation that reduces to prepare system; If in step (2) base oil is added thick product, then the preparation system of step (1) and step (2) is little, can effectively reduce and keep the required energy consumption of temperature of reaction.
Sequencing to low-carbon alcohol promotor and calcium oxide adding in the step (1) does not have particular requirement, but because the adding of low-carbon alcohol promotor and the reaction of calcium oxide and heavy alkylbenzene sulfonic acid are exothermic process, to note the temperature of reaction of controlled oxidation calcium and heavy alkylbenzene sulfonic acid especially, make it below boiling point that remains on low-carbon alcohol promotor, avoid low-carbon alcohol promotor to overflow in a large number and cause reaction efficiency to reduce.
The order of addition(of ingredients) of low-carbon alcohol promotor, secondary accelerator, alkaline earth metal halide and mixed-alkali calcium salt does not have influence to the performance of target product in the step (2).
Step (3) is a post-processing stages, the method that is adopted is ordinary method, for example, adopt the method for centrifugal, suction filtration or press filtration to separate solid residue in the thick product, adopt underpressure distillation to remove non-polar solvent, low-carbon alcohol promotor, secondary accelerator and water, the temperature of underpressure distillation is 50～70 ℃; Simultaneously, also can under 120～150 ℃, remove non-polar solvent, low-carbon alcohol promotor, secondary accelerator and water by the mode of air distillation.
Described heavy alkylbenzene sulfonic acid is through SO 3 sulfonated making by the high boiling point by-products produced heavy alkyl benzene that produces in the industrial production alkylbenzene process, the massfraction that contains the activeconstituents of sulfonic acid group is 75%～85%, molecular weight is preferably 400～600, is preferably 450～500 especially; The non-active ingredient of being introduced by heavy alkylbenzene sulfonic acid does not have influence to the result of use of target product.
Suitable non-polar solvent is short chain alkanes, alkyl-substituted aromatic hydrocarbon or its mixture, is preferably normal hexane, normal heptane, octane, nonane, 120# solvent oil, 180# solvent oil, sherwood oil, toluene or dimethylbenzene.
Described low-carbon alcohol promotor is preferably methyl alcohol, ethanol or ethylene glycol.
Described secondary accelerator is preferably quadrol or ammoniacal liquor.
Described alkaline earth metal halide is preferably calcium chloride or magnesium chloride.
The mol ratio of carbonic acid gas and described mixed-alkali calcium salt is preferably 0.8～1.4: 1.
The invention has the beneficial effects as follows: preparation method of the present invention is by compact one-step synthesis process, effectively controlled the crystal formation and the particle size of lime carbonate in the product, avoided because of generating the settlement issues that the calcite crystallization causes, having obtained lime carbonate is the high base number heavy alkyl benzene calcium sulfonate purification agent of vaterite-type, and the utilization of materials height; Adopting the industrial by-products heavy alkylbenzene sulfonic acid is raw material, and preparation cost is low; Lime carbonate is vaterite-type in the high base number heavy alkyl benzene calcium sulfonate purification agent provided by the invention, granular size is 10～60nm, the alkali content height of product, viscosity is low, clarification is stable, be convenient to produce and transportation, low viscous characteristic makes it be easy to realize that base number surpasses the preparation of the overbased purification agent of 400mg KOH/g; Compare with unformed carbonic acid calcium, crystal form lime carbonate has better extreme pressure, wear resisting property, helps improving the frictional behaviour of purification agent.
Description of drawings
Fig. 1 is fourier infrared (FTIR) spectrogram of embodiment 1 product.
Fig. 2 is dynamic light scattering (DLS) spectrogram of embodiment 1 product.
Fig. 3 is transmission electron microscope (TEM) figure of embodiment 1 product.
Fig. 4 is fourier infrared (FTIR) spectrogram of Comparative Examples 1 product.
Embodiment
The invention will be further described below in conjunction with embodiment.
(1) preparation of heavy alkyl benzene calcium sulfonate solution: 230g heavy alkylbenzene sulfonic acid (wherein, active component content is 85wt%, and molecular weight is 500) is dissolved in the 680g dimethylbenzene stirring and evenly mixing; Be warming up to 35 ℃, add 30g methyl alcohol and 20g calcium oxide, stirring reaction 45min.
(2) high base number heavy alkyl benzene calcium sulfonate purification agent is synthetic: add 75g calcium oxide, 65g calcium hydroxide, 1g magnesium chloride, 0.5g quadrol and 40g methyl alcohol, stirring and evenly mixing in above-mentioned heavy alkyl benzene calcium sulfonate solution; Under 50 ℃, in reaction system, feed the 83g carbonic acid gas with the speed of 300mL/min and carried out quaternization; Reaction removes heating bath after finishing, and the 150SN base oil that adds 100g dilutes thick product.
(3) aftertreatment: the thick product after the dilution removes dimethylbenzene, methyl alcohol, quadrol and water in 150 ℃ of following normal pressures after solid remnants are removed in press filtration, can obtain target product.
At first, embodiment 1 product is analyzed.The Fourier infrared spectrum of product (FTIR) as shown in Figure 1, spectrogram is at 877cm
-1And 745cm
-1Vaterite crystalline characteristics absorption peak occurs, show that lime carbonate exists with the vaterite-type crystallized form in embodiment 1 product.
Fig. 2 is dynamic light scattering (DLS) figure of embodiment 1 product, and the mean diameter of product is 34.4nm, and distribution range is 23～52nm; Fig. 3 is transmission electron microscope (TEM) figure of embodiment 1 product, can know equally to observe the particle of particle diameter about 30nm from figure, and this is consistent with DLS result, and size distribution is more even.The performance of embodiment 1 product sees table 1 for details.
Embodiment 2
Raw material and operate substantially the same manner as Example 1ly, difference is: the consumption of carbonic acid gas is 120g, the performance that makes product is as shown in table 1.
Analyze by FTIR, product is at 877cm
-1And 745cm
-1Vaterite crystalline characteristics absorption peak occurs, show that lime carbonate exists with the vaterite-type crystallized form in embodiment 2 products.
The product performance of table 1 embodiment 1～2
Embodiment 3
(1) preparation of heavy alkyl benzene calcium sulfonate solution: 230g heavy alkylbenzene sulfonic acid (wherein, active component content is 75wt%, and molecular weight is 450) is dissolved in the 120# solvent oil of 550g stirring and evenly mixing; Be warming up to 40 ℃, add 40g ethylene glycol and 20g calcium oxide, stirring reaction 30min.
(2) high base number heavy alkyl benzene calcium sulfonate purification agent is synthetic: add 20g calcium oxide, 138g calcium hydroxide, 10g calcium chloride, 3.5g ammoniacal liquor and 15g ethylene glycol, stirring and evenly mixing in above-mentioned heavy alkyl benzene calcium sulfonate solution; Under 40 ℃, in reaction system, feed the 85g carbonic acid gas with the speed of 300mL/min and carried out quaternization; Reaction removes heating bath after finishing, and the 100SN base oil that adds 100g dilutes thick product.
(3) aftertreatment: with thick product centrifugal treating 5min under 3000r/min, behind the gained clear liquid suction filtration, be that underpressure distillation removes 120# solvent oil, ethylene glycol, ammoniacal liquor and water under 0.093～0.098MPa condition, can obtain target product in 60 ℃, vacuum tightness.
Analyze by FTIR, embodiment 3 products are at 877cm
-1And 745cm
-1Vaterite-type crystalline characteristics absorption peak all occurs, show that lime carbonate exists with the vaterite-type crystallized form in embodiment 3 products.Product performance see table 2 for details.
Embodiment 4
Raw material and operate substantially the same manner as Example 3ly, difference is: the calcium oxide consumption is 80g in the step (2), and the calcium hydroxide consumption is 57g, and the ethylene glycol consumption is 30g.
Analyze by FTIR, embodiment 4 products are at 877cm
-1And 745cm
-1Vaterite-type crystalline characteristics absorption peak all occurs, show that lime carbonate exists with the vaterite-type crystallized form in embodiment 3 products.Product performance see Table 2.
Raw material and operate substantially the same manner as Example 3ly, difference is: the calcium oxide consumption is 105g in the step (2), and the calcium hydroxide consumption is 24g, and the ethylene glycol consumption is 40g.
Analyze by FTIR, embodiment 5 products are at 877cm
-1And 745cm
-1Vaterite-type crystalline characteristics absorption peak all occurs, show that lime carbonate exists with the vaterite-type crystallized form in embodiment 3 products.Product performance see Table 2.
The product performance of table 2 embodiment 3～5
Embodiment 6
(1) preparation of heavy alkyl benzene calcium sulfonate solution: 200g heavy alkylbenzene sulfonic acid (wherein, active component content is 80wt%, and molecular weight is 500) is dissolved in the 550g normal heptane stirring and evenly mixing; Be warming up to 30 ℃, add 20g ethanol and 17g calcium oxide, stirring reaction 45min.
(2) high base number heavy alkyl benzene calcium sulfonate purification agent is synthetic: add 30g calcium oxide, 125g calcium hydroxide, 3g calcium chloride, 1g quadrol and 70g ethanol, stirring and evenly mixing to above-mentioned heavy alkyl benzene calcium sulfonate solution; Under 60 ℃, in reaction system, feed the 85g carbonic acid gas with the speed of 300mL/min and carried out quaternization; Reaction removes heating bath after finishing, and the 350SN base oil that adds 100g dilutes thick product.
(3) aftertreatment: the thick product after the dilution removes normal heptane, ethanol, quadrol and water in 150 ℃ of following normal pressures after solid remnants are removed in press filtration, can obtain target product.
Analyze by FTIR, embodiment 6 products are at 877cm
-1And 745cm
-1Vaterite-type crystalline characteristics absorption peak all occurs, show that lime carbonate exists with the vaterite-type crystallized form in embodiment 6 products.Product performance see Table 3.
Embodiment 7
Raw material and operate substantially the same manner as Example 6ly, difference is: in the step (1), add ethanol and calcium oxide, stirring reaction 30min down at 40 ℃; The ethanol consumption is 40g in the step (2), and crossing alkalization temperature is 50 ℃.
Analyze by FTIR, embodiment 7 products are at 877cm
-1And 745cm
-1Vaterite-type crystalline characteristics absorption peak all occurs, show that lime carbonate exists with vaterite-type in embodiment 6 products.Product performance see Table 3.
Embodiment 8
Raw material and operate substantially the same manner as Example 6ly, difference is: in the step (1), add ethanol and calcium oxide, stirring reaction 30min down at 50 ℃; The ethanol consumption is 25g in the step (2), and crossing alkalization temperature is 35 ℃.
Analyze by FTIR, embodiment 8 products are at 877cm
-1And 745cm
-1Vaterite-type crystalline characteristics absorption peak all occurs, show that lime carbonate exists with the vaterite-type crystallized form in embodiment 6 products.Product performance see Table 3.
The product performance of table 3 embodiment 6～8
Embodiment 9
(1) preparation of heavy alkyl benzene calcium sulfonate solution: 180g heavy alkylbenzene sulfonic acid (wherein, active component content is 80wt%, and molecular weight is 500) is dissolved in the mixed solution of 150SN base oil of 680g dimethylbenzene and 160g stirring and evenly mixing; Be warming up to 30 ℃, add 50g methyl alcohol and 15g calcium oxide, stirring reaction 45min.
(2) high base number heavy alkyl benzene calcium sulfonate purification agent is synthetic: add 85g calcium oxide, 75g calcium hydroxide, 6g calcium chloride, 1g ammoniacal liquor and 20g methyl alcohol, stirring and evenly mixing in above-mentioned heavy alkyl benzene calcium sulfonate solution; Under 50 ℃, carried out quaternization to reaction system feeding 95g carbonic acid gas with the speed of 300mL/min; Reaction removes heating bath after finishing, cooling.
(3) aftertreatment: the thick product after the dilution takes off dimethylbenzene, methyl alcohol, ammoniacal liquor and water in 150 ℃ of following normal pressures after solid remnants are removed in press filtration, can obtain target product.
Analyze by FTIR, there is 877cm in embodiment 9 products
-1And 745cm
-1Vaterite-type crystalline characteristics absorption peak, show that lime carbonate is the vaterite crystal formation in the product.Product performance are as follows: output, 583g; Residue, 13g; Total basicnumber, 394.4mgKOH/g; Kinematic viscosity under 100 ℃, 32.5mm
2/ s; Particle dia, 39.9nm.
(1) preparation of heavy alkyl benzene calcium sulfonate solution: 230g heavy alkylbenzene sulfonic acid (wherein, active component content is 80wt%, and molecular weight is 500) is dissolved in the 460g normal hexane stirring and evenly mixing; Be warming up to 45 ℃, add 30g ethanol and 20g calcium oxide, stirring reaction 30min.
(2) high base number heavy alkyl benzene calcium sulfonate purification agent is synthetic: add 85g calcium oxide, 32g calcium hydroxide, 4g magnesium chloride and 40g ethanol, stirring and evenly mixing in above-mentioned heavy alkyl benzene calcium sulfonate solution; Under 45 ℃, in reaction system, feed the 85g carbonic acid gas with the speed of 300mL/min and carried out quaternization; Reaction removes heating bath after finishing, and the 150SN base oil that adds 150g dilutes thick product.
(3) aftertreatment: the thick product after the dilution removes normal hexane, ethanol and water in 150 ℃ of following normal pressures after solid remnants are removed in press filtration, can obtain target product.
Analyze by FTIR, there is 877cm in embodiment 10 products
-1And 745cm
-1Vaterite-type crystalline characteristics absorption peak, show that lime carbonate is the vaterite crystal formation in the product.Product performance are as follows: output, 592g; Residue, 13g; Total basicnumber (TBN), 362.8mg KOH/g; Kinematic viscosity under 100 ℃, 85.0mm
2/ s; Mean diameter, 30.4nm.
Comparative Examples 1
(1) preparation of heavy alkyl benzene calcium sulfonate solution: 230g heavy alkylbenzene sulfonic acid (wherein, active component content is 85wt%, and molecular weight is 500) is dissolved in the 680g dimethylbenzene stirring and evenly mixing; Be warming up to 35 ℃, add 30g methyl alcohol and 20g calcium oxide and stir stirring reaction 45min.
(2) high base number heavy alkyl benzene calcium sulfonate purification agent is synthetic: add 75g calcium oxide, 65g calcium hydroxide, 1g magnesium chloride, 0.5g quadrol and 40g methyl alcohol, stirring and evenly mixing in above-mentioned heavy alkyl benzene calcium sulfonate solution; Under 50 ℃, in reaction system, feed the 65g carbonic acid gas with the speed of 300mL/min and carry out quaternization; Reaction removes heating bath after finishing, and the 150SN base oil that adds 100g dilutes thick product.
(3) aftertreatment: the thick product after the dilution removes dimethylbenzene, methyl alcohol, quadrol and water in 150 ℃ of following normal pressures after solid remnants are removed in press filtration, can obtain target product.
The FTIR of Comparative Examples 1 product as shown in Figure 4, as can be seen from Figure 4, at 862cm
-1The characteristic peak of unformed carbonic acid calcium appears in the place, and this shows that lime carbonate exists with amorphous forms in Comparative Examples 1 product, and its performance sees table 4 for details.
Comparative Examples 2
Raw material and operation and Comparative Examples 1 are basic identical, and difference is: the consumption of carbonic acid gas is 50g, and the mol ratio of carbonic acid gas and mixed-alkali calcium salt is 0.51, and product performance see Table 4.
Analyze by FTIR, there is 862cm in Comparative Examples 2 products
-1Unformed carbonic acid calcium charateristic avsorption band, show that lime carbonate exists with amorphous forms in Comparative Examples 2 products.
The product performance of table 4 Comparative Examples 1～2
From embodiment 1～10 and Comparative Examples 1～2 as can be seen, lime carbonate exists with the vaterite-type crystallization in the high base number heavy alkyl benzene calcium sulfonate purification agent product that the inventive method makes, granular size is 10～60nm in the product, product alkali content height, viscosity are low, and clarification is stable, the total basicnumber of embodiment 4 products is 409.5mg KOH/g, and 100 ℃ kinematic viscosity is 125.0mm
2/ s is convenient to produce and transportation; Residue is few in the preparation process, is 13g among the embodiment 10, only is equivalent to the 52wt% of residue in the Comparative Examples 1, is equivalent to the 25.5wt% of residue in the Comparative Examples 2, the raw material availability height.
Claims (10)
1. high base number heavy alkyl benzene calcium sulfonate purification agent, it is characterized in that: be made up of the vaterite-type calcium carbonate of 80～160 mass parts, the heavy alkyl benzene calcium sulfonate of 78～89 mass parts and the base oil of 40～90 mass parts, particle grain size is 10～60nm in this purification agent.
2. by the described high base number heavy alkyl benzene calcium sulfonate of claim 1 purification agent, it is characterized in that: described base oil is I class, II class or the III class base oil in the API classification.
3. by the described high base number heavy alkyl benzene calcium sulfonate of claim 2 purification agent, it is characterized in that: described base oil is 100SN, 150SN, 200SN or 350SN base oil.
4. the preparation method of any described high base number heavy alkyl benzene calcium sulfonate purification agent of claim 1～3 is characterized in that may further comprise the steps successively:
(1) preparation of heavy alkyl benzene calcium sulfonate solution: the heavy alkylbenzene sulfonic acid of 100 mass parts is dissolved in the non-polar solvent of 200～380 mass parts, under 30～50 ℃ of temperature, add the low-carbon alcohol promotor of 10～30 mass parts and the calcium oxide of 8～12 mass parts, and stirring reaction;
(2) high base number heavy alkyl benzene calcium sulfonate purification agent is synthetic: add the low-carbon alcohol promotor of 5～35 mass parts, the secondary accelerator of 0～1.5 mass parts, the alkaline earth metal halide of 0.5～4.5 mass parts and the mixed-alkali calcium salt of 50～90 mass parts in above-mentioned heavy alkyl benzene calcium sulfonate solution, mix, controlled temperature is 30～60 ℃, in system, feed carbonic acid gas and carried out quaternization, obtain thick product; Described mixed-alkali calcium salt is the mixture that calcium oxide and calcium hydroxide are formed, and the mass ratio of calcium oxide and calcium hydroxide is 1: 7～4.5: 1;
Wherein, adding total amount in one of step (1) and step (2) at least is the base oil of 40～90 mass parts: base oil added before low-carbon alcohol promotor and calcium oxide in the step (1), and was that base oil is added in the thick product in the step (2);
(3) aftertreatment: at first separate the solid residue of removing in the thick product, non-polar solvent, low-carbon alcohol promotor, secondary accelerator and water are removed in distillation then, can obtain target product.
5. press the preparation method of the described high base number heavy alkyl benzene calcium sulfonate of claim 4 purification agent, it is characterized in that: the massfraction that contains the activeconstituents of sulfonic acid group in the described heavy alkylbenzene sulfonic acid is 75%～85%, molecular weight is 400～600, and molecular weight is preferably 450～500.
6. by the preparation method of the described high base number heavy alkyl benzene calcium sulfonate of claim 4 purification agent, it is characterized in that: described non-polar solvent is normal hexane, normal heptane, octane, nonane, 120# solvent oil, 180# solvent oil, sherwood oil, toluene or dimethylbenzene.
7. by the preparation method of the described high base number heavy alkyl benzene calcium sulfonate of claim 4 purification agent, it is characterized in that: described low-carbon alcohol promotor is methyl alcohol, ethanol or ethylene glycol.
8. by the preparation method of the described high base number heavy alkyl benzene calcium sulfonate of claim 4 purification agent, it is characterized in that: described secondary accelerator is quadrol or ammoniacal liquor.
9. by the preparation method of the described high base number heavy alkyl benzene calcium sulfonate of claim 4 purification agent, it is characterized in that: described alkaline earth metal halide is calcium chloride or magnesium chloride.
10. by the preparation method of any described high base number heavy alkyl benzene calcium sulfonate purification agent of claim 4～9, it is characterized in that: the mol ratio of carbonic acid gas and described mixed-alkali calcium salt is 0.8～1.4: 1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105503670A (en) * | 2016-01-12 | 2016-04-20 | 安徽金桐精细化学有限公司 | High-alkaline-value synthetic calcium alkyl benzene sulfonate nano detergent and preparation method thereof |
| CN105505523A (en) * | 2015-12-20 | 2016-04-20 | 仇颖超 | Method for preparing compounded lubricating oil detergent on basis of modified calcite |
| CN107118137A (en) * | 2017-06-26 | 2017-09-01 | 锦州康泰润滑油添加剂股份有限公司 | Heavy alkyl benzene zinc sulfonate as oil product antirust agent and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2937991A (en) * | 1956-12-19 | 1960-05-24 | Continental Oil Co | Method of dispersing calcium carbonate in a non-volatile carrier |
| CN1334325A (en) * | 2000-07-19 | 2002-02-06 | 中国石油天然气股份有限公司兰州炼化分公司 | Process for preparing ultrahigh-basicity composite metal detergent |
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2011
- 2011-07-25 CN CN2011102088314A patent/CN102295971A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2937991A (en) * | 1956-12-19 | 1960-05-24 | Continental Oil Co | Method of dispersing calcium carbonate in a non-volatile carrier |
| CN1334325A (en) * | 2000-07-19 | 2002-02-06 | 中国石油天然气股份有限公司兰州炼化分公司 | Process for preparing ultrahigh-basicity composite metal detergent |
Non-Patent Citations (2)
| Title |
|---|
| ZHAOCONG CHEN, ET AL.: "Calcium carbonate phase transformations during the carbonation reaction of calcium heavy alkylbenzene sulfonate overbased nanodetergents preparation", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| 张景河: "润滑油清净分散剂金属化工艺方法的发展", 《石油炼制》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105505523A (en) * | 2015-12-20 | 2016-04-20 | 仇颖超 | Method for preparing compounded lubricating oil detergent on basis of modified calcite |
| CN105503670A (en) * | 2016-01-12 | 2016-04-20 | 安徽金桐精细化学有限公司 | High-alkaline-value synthetic calcium alkyl benzene sulfonate nano detergent and preparation method thereof |
| CN107118137A (en) * | 2017-06-26 | 2017-09-01 | 锦州康泰润滑油添加剂股份有限公司 | Heavy alkyl benzene zinc sulfonate as oil product antirust agent and preparation method thereof |
| CN107118137B (en) * | 2017-06-26 | 2021-10-29 | 锦州康泰润滑油添加剂股份有限公司 | Heavy alkyl benzene zinc sulfonate as oil product antirust agent and preparation method thereof |
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Application publication date: 20111228 |