CN103725355B - Preparation method of low-base number lubricating oil clearing agent - Google Patents
Preparation method of low-base number lubricating oil clearing agent Download PDFInfo
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Abstract
The invention provides a preparation method of a low-base number lubricating oil clearing agent. The method of the invention comprises the following steps: (1) mixing and stirring organic sulfur phosphonic acid, alkylphenol and/or sulfurized alkylphenol, particle activated carbon, and aqueous solution of low molecular alcohol, separating and recovering an oil-phase product; (2) adding oxides of alkaline earth metal, water, inorganic acid and/or aryl carboxylic acid promoters in the oil-phase product of step (1), performing a metallization reaction, and collecting the product. The clearing agent obtained by the method of the invention has good oxidation resistance, high-temperature clearing performance, less toxin, and less smell, and is a lubricating oil additive with comprehensive performance.
Description
Technical field
The present invention relates to a kind of detergent for lubricating oil, particularly a kind of preparation method of low alkali value detergent for lubricating oil.
Background technology
Polyisobutene phosphine sulfide salt additives develops a class purification agent comparatively early, and traditional phosphine sulfide hydrochlorate take barium salt as metal, and product has detergency dispersed and certain preferably, but its thermostability has certain limitation.
Research report about polyisobutene phosphine sulfide acid barium is more, patent GB 1004401 and US 3377282 describes the preparation method of phosphine sulfide acid barium, its method is by mixing phosphine sulfide polyisobutene and alkylphenol or sulfenyl phenolate reaction, then with the oxide compound of divalent metal or oxyhydroxide reaction, the alkyl wherein connecting alkylphenol or sulfenyl phenolate is 5-20 carbon atom, and the molecular weight of polyisobutene is 500-3500.
US 3135729 describes the product reacted at polyisobutene and thiophosphoric anhydride and is hydrolyzed in phosphine sulfide acid and adds barium oxide again, pass into carbon dioxide reaction and obtain the barium salt that barium content is 7%, but polyisobutene phosphine sulfide acid barium salt toxicity is comparatively large, has greater environmental impacts, therefore not regenerative ratio.What substitute polyisobutene phosphine sulfide acid barium salt is polyisobutene phosphine sulfide acid calcium salt and magnesium salts, and the two is except toxicity is lower, also has detergency dispersed and certain preferably.
Research report about polyisobutene phosphine sulfide acid calcium salt and magnesium salts is more, the preparation method of sulphur phosphorus hydrocarbon derivative is such as described at patent GB 910738, namely react when formaldehyde or ketone promotor exist with hydrolysis sulphur phosphorus hydrocarbon and alkaline earth metal compound, its product can be tested by the detergency of CRC L-1.
GB 1039732 describes the preparation method of polyisobutene phosphine sulfide hydrochlorate purification agent, in the sulfur-bearing alkyl of acidity, phenol and inert solvent, add and be less than stoichiometric basic metal or alkaline-earth metal, then in high temperature, pass into carbonic acid gas form colloidal-carbon hydrochlorate, need water in carbonation reaction, add sulphur after carbonation reaction terminates and carry out vulcanization reaction.
GB 1177835 describes high alkalinity purification agent preparation method, and the method is to pass into carbonic acid gas after the reactant mixing such as sulfenyl phenolate, thiophosphoric anhydride, polyolefine, amine, calcium oxide, calcium hydroxide, alkoxide.
US 3321399 describes the preparation of oil-soluble metal carbonate, comprises with phosphine sulfide polyolefine, nonyl phenol, calcium hydroxide, urea, mineral oil, water for raw material reaction.
Patent GB 910738, US 313572, US 3706665 with the polyisobutene of molecular weight 780-1100 for raw material, patent GB 103972, GB 1004401, US 3377282, GB 1177835, US 3135729 with polyisobutene and a small amount of alkylphenol for raw material, although the product of preparation has certain detergency, still lower compared with alkyl benzene calcium sulfonate, calcium sulfenyl phenolate, alkyl sodium salicylate.
Summary of the invention
The invention provides a kind of preparation method of low alkali value detergent for lubricating oil.
The inventive method comprises:
(1) aqueous solution of organic sulfur phosphonic, alkylphenol and/or sulfenyl phenolate, granulated active carbon and low mass molecule alcohol is stirred, Separation and Recovery oil-phase product;
(2) in the oil-phase product of step (1), add the oxide compound of alkaline-earth metal, water, mineral acid and/or aryl carboxylic acid promotor, carry out metallization reaction, collect product.
The structure of the organic sulfur phosphonic described in step (1) is:
Wherein R
1for the alkyl of number-average molecular weight between 500-5000, preferred 700-3500, most preferably 850-2500; X is O atom or S atom, and wherein at least one X is S atom, the preferred S atom of X.
Organic sulfur phosphonic described in step (1) is obtained by reacting by polyolefine generation phosphine sulfide, and namely polyolefine and thiophosphoric anhydride and/or sulphur phosphatase reaction obtain.Described polyolefine is by ethene, propylene, C
4-C
10alkene is polymerized separately or copolymerization and the polyolefine obtained, described C
4-C
10alkene can select in n-butene, iso-butylene, positive amylene, n-hexylene, positive octene and positive decene one or more, preferred polyisobutene.Described polyolefinic number-average molecular weight is 500-5000, preferred 700-3500, most preferably 850-2500.The temperature of described phosphine sulfideization reaction is between 100-300 DEG C, and preferred 150-250 DEG C, the reaction times is 5h ~ 20h, preferred 12h ~ 18h.
The preferred methylene-bridged alkylphenol of alkylphenol described in step (1), its structural formula is:
Wherein R
2for C
4-C
30alkyl, preferred C
6-C
20alkyl, most preferably C
8-C
15alkyl.
The preparation method of described methylene-bridged alkylphenol is: by alkylphenol, aqueous sodium hydroxide solution mixing, stir and heat up, formaldehyde is dripped 50 DEG C time, 80-90 DEG C of isothermal reaction 3 hours are warmed up to after adding, then 150 DEG C are warmed up to, remove water and unreacted formaldehyde, obtain methylene-bridged alkylphenol.
Described in step (1), the structure of sulfenyl phenolate is:
Wherein R
2for C
4-C
30alkyl, preferred C
6-C
20alkyl, most preferably C
8-C
15alkyl; N is the integer between 1-10, preferred 1-7, most preferably 1-4.
Sulfenyl phenolate described in step (1) is normally obtained by reacting under promotor exists by vulcanizing agent and abovementioned alkyl phenol, one or more normally in sulphur, sulfur dichloride and sulfur subchloride of described vulcanizing agent, described promotor generally includes organo-peroxide and/or polysulphide polymer, such as benzoyl peroxide and/or 2-mercaptobenzothiazole.
Described in step (1), the preferred specific surface area of granulated active carbon is at 700-2000m
2the granulated active carbon of/g, most preferably specific surface area is at 900-1100m
2the granulated active carbon of/g.
Low mass molecule alcohol described in step (1) is selected from the monohydroxy-alcohol of carbonatoms between 1-8 or polyvalent alcohol, adducible example includes but not limited to methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, octanol, enanthol, ethylene glycol, propylene glycol, the monohydroxy-alcohol of preferred carbonatoms between 1-4, one or more in most preferred ethanol, propyl alcohol and butanols.
In the aqueous solution of low mass molecule alcohol described in step (1), low mass molecule alcohol accounts for the 5%-50% of aqueous solution total mass, preferred 10%-40%, most preferably 15%-30%.
Mol ratio between organic sulfur phosphonic described in step (1) and described alkylphenol and/or sulfenyl phenolate is 1:10 ~ 10:1, preferred 1:6 ~ 6:1, most preferably 1:4 ~ 4:1.
Granulated active carbon described in step (1) is the 5-50% of organic sulfur phosphonic and described alkylphenol and/or sulfenyl phenolate quality sum, preferred 10-40%, most preferably 15-35%.
Mass ratio described in step (1) between granulated active carbon and low mass molecule alcohol solution is 1:15-1:50, preferred 1:20-1:40.
Step can not add solvent in (1), also can add solvent.Described solvent is the hydro carbons of boiling range between 80-200 DEG C, can be simple substance hydrocarbon, also can be hydrocarbon mixture, can select normal heptane, octane, No. 120 industrial napthas, No. 200 industrial napthas and boiling ranges are one or more in the sherwood oil of 90-120 DEG C.The quality of described solvent is the 50-200% of organic sulfur phosphonic and described alkylphenol and/or sulfenyl phenolate quality sum, preferred 60-150%, most preferably 70-120%.
In step (1), the temperature of mix and blend is between 10-50 DEG C, and preferred 30-40 DEG C, the time of mix and blend is 0.5-10 hour, preferred 1-5 hour.
One or more in the oxide compound preferential oxidation magnesium of the alkaline-earth metal described in step (2), calcium oxide, strontium oxide and barium oxide, most preferably calcium oxide and/or magnesium oxide.
The mole number of the oxide compound of alkaline-earth metal described in step (2) is the 1:10 ~ 10:1 of the mole number sum of organic sulfur phosphonic and described alkylphenol and/or sulfenyl phenolate described in step (1), preferred 1:5 ~ 5:1, most preferably 1:4 ~ 4:1.
In step (2), the mol ratio of the oxide compound of water and alkaline-earth metal is 1:4 ~ 6:1, preferred 1:2 ~ 4:1, most preferably 1:1 ~ 3:1.
Described in step (2), mineral acid can select one or more in sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid, preferably sulfuric acid; Described aryl carboxylic acid comprises aryl monoprotic acid and/or aryl diprotic acid, described aryl is phenyl and/or naphthyl, aryl dicarboxylic acid comprise neighbour, contraposition aryl dicarboxylic acid, described aryl carboxylic acid can select phenylformic acid, naphthoic acid, phthalic acid, m-phthalic acid, terephthalic acid, adjacent naphthalic acid, a naphthalic acid and to one or more in naphthalic acid.
The 0.1-10% that mineral acid described in step (2) and/or aryl carboxylic acid promotor are organic sulfur phosphonic described in step (1) and described alkylphenol and/or sulfenyl phenolate quality sum, preferred 0.5-6%, most preferably 1-3%.
Step can not add thinning oil in (2), also can add thinning oil.Described thinning oil is that 100 DEG C of kinematic viscosity are at 2-10mm
2the lubricating base oil of/s can be solvent treatment lubricating base oil, also can be hydrofining lubricating base oil, can select one or more in I class, II class, III class and IV class lubricating base oil.Described thinning oil accounts for the 30-150% of organic sulfur phosphonic and described alkylphenol and/or sulfenyl phenolate quality sum, preferred 50-120%, most preferably 70-100%.
Described in step (2), the temperature of metallization reaction is 20 ~ 200 DEG C, preferably 40 ~ 160 DEG C, most preferably 60 ~ 120 DEG C.
The time of metallization reaction described in step (2) is 1 ~ 10 hour, preferably 2 ~ 8 hours, most preferably 3 ~ 6 hours.
Filter the product of step (2) metallization reaction, remove unreacted solid residue, then distillation collects product except after desolventizing or promotor.
The purification agent utilizing the inventive method to obtain has good oxidation-resistance, high temperature detergency, and its toxicity is little, smell is little, is the comprehensive lubricating oil additive of a kind of performance.
Embodiment
Further describe the present invention below by example, but the present invention is not limited to this.
The preparation of organic sulfur phosphonic A
The polyisobutene 1000 grams that number-average molecular weight is 750 is added in the there-necked flask being provided with electric stirring, add P2S5168 gram, be warmed up to 210 DEG C gradually from room temperature, heat-up rate, at 30 DEG C/h, is warmed up to rear constant temperature 12 hours, now material gradually becomes brown from colourless, pass into 8.5 grams of water vapors after reaction to react, and carry out aftertreatment, the polyisobutene phosphine sulfide acid sulphur content obtained is 5.2%, phosphorus content is 2.2%, is designated as organic sulfur phosphonic A.
The preparation of organic sulfur phosphonic B
In the there-necked flask being provided with electric stirring, add the polyisobutene 1000 grams of number-average molecular weight 1300, add P
2s
5140 grams, be warmed up to 223 DEG C gradually from room temperature, heat-up rate 30 DEG C/h, be warmed up to rear constant temperature 11 hours, now material gradually becomes brown from colourless, passes into 8 grams of water vapors and reacts, and carry out aftertreatment.The polyisobutene phosphine sulfide acid sulphur content obtained is 4.8%, and phosphorus content is 1.7%, is designated as organic sulfur phosphonic B.
The synthesis of sulfenyl phenolate
4-dodecylphenol 1710 grams is added in that be provided with electric stirring, the airtight there-necked flask with hydrogen sulfide absorption device, add SULPHUR POWDER 145 grams, sulphurized catalyst 2-mercaptobenzothiazole 3 grams, ethylene glycol 100 grams, be warmed up to 160 DEG C of reactions 12 hours, after reaction terminates, steam ethylene glycol, sedimentation, obtain sulfuration 4-dodecylphenol FDDP, sulphur content is 5.3%.
The synthesis of methylene-bridged alkylphenol
4-dodecylphenol 1000 grams is added in the there-necked flask being provided with electric stirring, the aqueous sodium hydroxide solution of 20% 20 grams, stir and heat up, add 352 grams, the formaldehyde of 37%, 50 DEG C time, drip formaldehyde, after adding, be warmed up to reflux temperature, i.e. 80-90 DEG C of isothermal reaction 3 hours, then be warmed up to 150 DEG C, remove water and unreacted formaldehyde, obtain the MDDP containing methylene-bridged 4-dodecylphenol.
Adopt the raw material of above synthesis, synthesize purification agent of the present invention, specific embodiment is as follows:
Embodiment 1 (mol ratio of organic sulfur phosphonic A and sulfuration 4-dodecylphenol is 1:3.1)
In the 3000ml there-necked flask being provided with temperature control system and electric stirring; add organic sulfur phosphonic A 40 grams of (molecular weight 1112; 0.036mol); add sulfuration 4-dodecylphenol 60 grams of (molecular weight 554 again; 0.11mol), 100 grams of 90-120 DEG C of sherwood oils, stir 15 minutes; (traditional Chinese medicines group produces, and specific surface area is 900-1100m to add 30 grams of grain active carbons again
2/ g) and the aqueous ethanolic solution of 1000 gram 20%.The temperature controlling there-necked flask is 20-30 DEG C, and mix and blend stopped after 4 hours, separated the oil phase on upper strata, was about 194 grams, and aqueous phase is the used ethanolic soln containing grain active carbon.
Separate above 194 grams of oil phases are incorporated with in the 500ml there-necked flask of temperature control system and electric stirring, then 90 grams of 150SN neutral oils are added, add 4.4 grams of calcium oxide (0.079mol), 2.5 grams, water (0.139mol), 2.0 gram of 98% vitriol oil, controlling temperature of reaction is 100 DEG C, react 5 hours, then water is steamed, material is cooled to 50 DEG C, at rotating speed be 2000rpm whizzer on centrifugal 30 minutes, distill after removing slag, obtain low alkali value purification agent Ca-1, smell is less, its base number is 40.2mgKOH/g, sulphur content is 2.5%, phosphorus content is 0.43%.
Embodiment 2 (mol ratio of organic sulfur phosphonic B and methylene-bridged 4-dodecylphenol is 1:2.9)
In the 3000ml there-necked flask being provided with temperature control system and electric stirring, (molecular weight is 2341 to add organic sulfur phosphonic B 60 grams, 0.026mol), (molecular weight is 536 to add methylene-bridged 4-dodecylphenol 40 grams again, 0.075mol), 100 grams of octanes, stir 15 minutes, add grain active carbon 25 grams again, 25% aqueous ethanolic solution 1000 grams, at 20-30 DEG C of mix and blend, controlling stirring velocity makes the interface of oil phase and aqueous phase occur all the time, mix and blend is after 4 hours, the oil phase on upper strata is separated, about 196 grams, aqueous phase is the used aqueous ethanolic solution containing grain active carbon.
Separate above 196 grams of oil phases are incorporated with in the 500ml there-necked flask of temperature control system and electric stirring, then 95 grams of 150SN neutral oils are added, add 4.5 grams of calcium oxide (0.080mol), 1.5 grams, water (0.083mol), 2.2 grams of phenylformic acid, controlling temperature of reaction is 100 DEG C, react 5 hours, then steam water, material is cooled to 50 DEG C, at rotating speed be 2000rpm whizzer on centrifugal 30 minutes, distill after removing slag, obtain low alkali value purification agent Ca-2, smell is less, its base number is 39.6mgKOH/g, and sulphur content is 1.45%; Phosphorus content is 0.51%.
Embodiment 3 (ratio of the mole number of organic sulfur phosphonic A and sulfuration 4-dodecylphenol and methylene-bridged 4-dodecylphenol mole number sum is 1.1)
In the 3000ml there-necked flask being provided with temperature control system and electric stirring, add organic sulfur phosphonic A70 gram of (molecular weight 1112, 0.063mol), add sulfuration 4-dodecylphenol 15 grams of (molecular weight 554 again, 0.027mol), methylene-bridged 4-dodecylphenol 15 grams of (molecular weight 536, 0.028mol), 90 grams of No. 200 industrial napthas, stir 15 minutes, add grain active carbon 28 grams again, 30% aqueous ethanolic solution 960 grams, at 20-30 DEG C of mix and blend, now stirring velocity should be controlled, the interface of oil phase and aqueous phase is occurred all the time, mix and blend is after 4 hours, the oil phase on upper strata is separated, about 187 grams, aqueous phase is the used aqueous ethanolic solution containing grain active carbon.
Separate above 175 grams of oil-phase product are incorporated with in the 500ml there-necked flask of temperature control system and electric stirring, then 70 grams of 150SN neutral oils are added, add 4.5 grams of calcium oxide (0.080mol), 2.2 grams of water (0.122mol), add 1.9 grams of phthalic acids, controlling temperature of reaction is 100 DEG C, react 5 hours, then steam water, material is cooled to 50 DEG C, at rotating speed be 2000rpm whizzer on centrifugal 30 minutes, distill after removing slag, obtain low alkali value purification agent Ca-3, smell is less, its base number is 39.2mgKOH/g, and sulphur 2.6 content is %; Phosphorus content is 0.85%.
Embodiment 4 (mol ratio of organic sulfur phosphonic A and methylene-bridged 4-dodecylphenol is 2.6:1)
In the 3000ml there-necked flask being provided with temperature control system and electric stirring, add organic sulfur phosphonic A80 gram of (molecular weight 1112, 0.072mol), add methylene-bridged 4-dodecylphenol 20 grams of (molecular weight 536 again, 0.028mol), 90 grams of No. 200 industrial napthas, stir 15 minutes, add grain active carbon 32 grams again, 22% ethanolic soln 1050 grams, at 20-30 DEG C of mix and blend, now stirring velocity should be controlled, the interface of oil phase and aqueous phase is occurred all the time, mix and blend is after 4 hours, the oil phase on upper strata is separated, about 187 grams, aqueous phase is the used aqueous ethanolic solution containing grain active carbon.
Separate above 187 grams of oil phases are incorporated with in the 500ml there-necked flask of temperature control system and electric stirring, then 90 grams of 150SN neutral oils are added, add 3.2 grams of magnesium oxide (0.08mol), 2.2 grams, water (0.12mol), 2.2 grams of vitriol oils (98%), controlling temperature of reaction is 100 DEG C, react 5 hours, then water is steamed, material is cooled to 50 DEG C, at rotating speed be 2000rpm whizzer on centrifugal 30 minutes, distill after removing slag, obtain low alkali value purification agent Mg-1, smell is less, its base number is 46.2mgKOH/g, sulphur content is 2.2%, phosphorus content is 0.92%.
Comparative example 1 (mol ratio of organic sulfur phosphonic A and sulfuration 4-dodecylphenol is 1:3.1)
In the 500ml there-necked flask being provided with temperature control system and electric stirring, add organic sulfur phosphonic A 40 grams of (molecular weight 1112, 0.036mol), add sulfuration 4-dodecylphenol 60 grams of (molecular weight 554 again, 0.11mol), 100 grams of 90-120 DEG C of sherwood oils, stir 15 minutes, then 90 grams of 150SN neutral oils are added, add 4.4 grams of calcium oxide (0.078mol), 2.5 grams, water (0.139mol), 2.0 gram of 98% vitriol oil, controlling temperature of reaction is 100 DEG C, react 5 hours, then water is steamed, material is cooled to 50 DEG C, at rotating speed be 2000rpm whizzer on centrifugal 30 minutes, distill after removing slag, obtain contrast low alkali value purification agent DCa-1, smell is larger, its base number is 40.1mgKOH/g, sulphur content is 2.6%, phosphorus content is 0.44%.
Comparative example 2-4
Similar to embodiment 2-4 respectively, just in step (1), do not add gac and aqueous ethanolic solution, and do not have mixing process, other reaction conditions is identical, prepare contrast low alkali value purification agent DCa-2, DCa-3, DCa-4 thus respectively.DCa-2 smell is comparatively large, and its base number is 39.7mgKOH/g, and sulphur content is 1.45%, and phosphorus content is 0.52%; DCa-3 smell is large, and its base number is 39.2mgKOH/g, and sulphur content is 2.6%, and phosphorus content is 0.86%; DCa-4 smell is large, and its base number is 46.3mgKOH/g, and sulphur content is 2.3%, and phosphorus content is 0.92%.
The purification agent prepared embodiment 1-4 and comparative example 1-4 carries out the qualification test of high temperature detergency, anti-oxidative stability, and evaluation method is as follows:
Lacquering and the experiment of coking plate is adopted to evaluate high temperature detergency:
L-1 plate-type coking device carries out lacquering and the experiment of coking plate.Coke test condition is: plate temperature/oil temperature=320 DEG C/100 DEG C, time 2 h, stop/ETAD expected time of arrival and departure=45 second/15 seconds.Lacquering test conditions is: plate temperature/oil temperature=300 DEG C/150 DEG C, time 2 h, operates continuously.
L-A type detergency tester is tested, to investigate its high temperature detergency.Test conditions is: plate temperature/oil temperature=300 DEG C/100 DEG C, 1 hour time, stop/ETAD expected time of arrival and departure=40 second/20 seconds.Oil droplet speed is 1.0mL/min.
Anti-oxidative stability evaluation adopts PDSC (Pressure Differential Scanning Calorimeter pressure means of differential scanning calorimetry) method, and testing installation is TA5000 DSC2910 thermal analyzer.
By 150SN, 500SN, 150BS is modulated into lubricating base oil by the mass ratio of 14:5:1, purification agent in embodiment 1-4 and comparative example 1-4 is called in lubricating base oil with the add-on of 2% the embodiment 5-8 and comparative example 5-8 that obtain lubricating composition respectively, carry out above-mentioned qualification test to investigate the various performances of purification agent to these lubricating compositions, test-results is in table 1.
As can be seen from Table 1, in High Temperature Detergent Experiment, coking amount, the lacquering amount of embodiment 5-8 are less, and coking amount in comparative example 5-8 and lacquering amount larger.In PDSC test, the oxidation induction period of embodiment 5-8 is slightly long relative to the oxidation induction period of comparative example 5-8, illustrates that its oxidation-resistance is better.The smell of embodiment 5-8 is significantly less than comparative example 5-8.
In sum, the purification agent utilizing the inventive method to obtain has good oxidation-resistance, high temperature detergency, and its toxicity is little, smell is little, is the comprehensive lubricating oil additive of a kind of performance.
Table 1 assessment of performance result
Claims (16)
1. a preparation method for low alkali value detergent for lubricating oil, comprising:
(1) aqueous solution of organic sulfur phosphonic, alkylphenol and/or sulfenyl phenolate, granulated active carbon and low mass molecule alcohol is stirred, Separation and Recovery oil-phase product;
The structure of described organic sulfur phosphonic is:
Wherein R
1for the alkyl of number-average molecular weight between 500-5000, X is O atom or S atom, and wherein at least one X is S atom;
Described alkylphenol is methylene-bridged alkylphenol, and its structural formula is:
The structure of described sulfenyl phenolate is:
Wherein R
2for C
4-C
30alkyl; N is the integer between 1-10;
Described low mass molecule alcohol is selected from the monohydroxy-alcohol of carbonatoms between 1-8 or polyvalent alcohol;
Mol ratio between described organic sulfur phosphonic and described alkylphenol and/or sulfenyl phenolate is 1:10 ~ 10:1;
(2) in the oil-phase product of step (1), add the oxide compound of alkaline-earth metal, water, mineral acid and/or aryl carboxylic acid promotor, carry out metallization reaction, collect product;
The mole number of the oxide compound of described alkaline-earth metal is the 1:10 ~ 10:1 of the mole number sum of organic sulfur phosphonic and described alkylphenol and/or sulfenyl phenolate described in step (1); The 0.1-10% that described mineral acid and/or aryl carboxylic acid promotor are organic sulfur phosphonic described in step (1) and described alkylphenol and/or sulfenyl phenolate quality sum.
2. in accordance with the method for claim 1, it is characterized in that, described in step (1), the specific surface area of granulated active carbon is 700-2000m
2/ g.
3. in accordance with the method for claim 1, it is characterized in that, in the aqueous solution of low mass molecule alcohol described in step (1), low mass molecule alcohol accounts for the 5%-50% of aqueous solution total mass.
4. in accordance with the method for claim 1, it is characterized in that, the mol ratio between organic sulfur phosphonic described in step (1) and described alkylphenol and/or sulfenyl phenolate is 1:6 ~ 6:1.
5. in accordance with the method for claim 1, it is characterized in that, granulated active carbon described in step (1) is the 5-50% of organic sulfur phosphonic and described alkylphenol and/or sulfenyl phenolate quality sum.
6. in accordance with the method for claim 1, it is characterized in that, the mass ratio described in step (1) between granulated active carbon and low mass molecule alcohol solution is 1:15-1:50.
7. in accordance with the method for claim 1, it is characterized in that, step adds solvent in (1), and described solvent is the hydro carbons of boiling range between 80-200 DEG C, and the quality of described solvent is the 50-200% of organic sulfur phosphonic and described alkylphenol and/or sulfenyl phenolate quality sum.
8. in accordance with the method for claim 1, it is characterized in that, in step (1), the temperature of mix and blend is between 10-50 DEG C, and the time of mix and blend is 0.5-10 hour.
9. in accordance with the method for claim 1, it is characterized in that, the oxide compound of the alkaline-earth metal described in step (2) is one or more in magnesium oxide, calcium oxide, strontium oxide and barium oxide.
10. in accordance with the method for claim 1, it is characterized in that, the mole number of the oxide compound of alkaline-earth metal described in step (2) is the 1:5 ~ 5:1 of the mole number sum of organic sulfur phosphonic and described alkylphenol and/or sulfenyl phenolate described in step (1).
11. in accordance with the method for claim 1, it is characterized in that, in step (2), the mol ratio of the oxide compound of water and alkaline-earth metal is 1:4 ~ 6:1.
12. in accordance with the method for claim 1, it is characterized in that, mineral acid described in step (2) is one or more in sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid; Described aryl carboxylic acid comprises aryl monoprotic acid and/or aryl diprotic acid, and described aryl is phenyl and/or naphthyl.
13. in accordance with the method for claim 1, it is characterized in that, described aryl carboxylic acid selects phenylformic acid, naphthoic acid, phthalic acid, m-phthalic acid, terephthalic acid, adjacent naphthalic acid, a naphthalic acid and to one or more in naphthalic acid.
14. in accordance with the method for claim 1, it is characterized in that, the 0.5-6% that mineral acid described in step (2) and/or aryl carboxylic acid promotor are organic sulfur phosphonic described in step (1) and described alkylphenol and/or sulfenyl phenolate quality sum.
15. in accordance with the method for claim 1, it is characterized in that, step adds thinning oil in (2), and described thinning oil is that 100 DEG C of kinematic viscosity are at 2-10mm
2the lubricating base oil of/s, described thinning oil accounts for the 30-150% of organic sulfur phosphonic and described alkylphenol and/or sulfenyl phenolate quality sum.
16. in accordance with the method for claim 1, it is characterized in that, described in step (2), the temperature of metallization reaction is 20 ~ 200 DEG C, and the time of metallization reaction is 1 ~ 10 hour.
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| US3377282A (en) * | 1965-09-13 | 1968-04-09 | Monsanto Chemicals | Production of oil additives |
| CN101423483B (en) * | 2008-06-20 | 2012-08-01 | 辽宁天合精细化工股份有限公司 | High basic value (TBN400) sulfurized calcium alkyl and preparation method thereof |
| CN102071085B (en) * | 2009-11-19 | 2013-01-30 | 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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