The compound pour point depressant of lubricating oil and preparation method
technical field
The present invention relates to a kind of lubricating oil additive, i.e. the compound pour point depressant of lubricating oil and preparation method.Trade name: bar figure board 2014 type pour depressant for lubricating oil.
Background technology
The pour point depression mechanism of pour depressant for lubricating oil: well-known, about pour point depression mechanism, mainly exist theoretical two kinds of nucleation theory and eutectic.Eutectic theoretical explanation dibehenyl fumarate-vinyl acetate copolymer is more reasonable to the pour-point depressing process of naphthenic lube oil.When not with pour point depressant, solidifying crystal is two-dimensional growth, and the growth velocity of X, Y direction is too fast, and crystallization grows up to diamond platy, while growing up to 200 μ m left and right, connects to net, has destroyed the mobility of oil product.Add after common pour point depressant, due to the long carbon side chain of T818C pour point depressant molecule and cycloalkyl molecule, middle short-side chain and paraffinic base molecule structurally have enough similaritys, and enter in the lattice of crystallization, replaced original nucleus in lattice and eutectic has occurred.But because of the polar portion in T818C pour point depressant molecule from solidify different in crystal molecule, hinder the growth of crystallization in X, Y direction, but relatively accelerated the speed of growth of crystallization in Z-direction, also changed the shape of crystallization, make crystal gradually towards the many ingotism future developments of branch simultaneously.After T818C pour point depressant adds, in promoting that crystallization is grown to Z-direction, suppressed to the growth of X, Y direction, crystal formation is changed to rectangular pyramid, four prism type by irregular bulk.This crystal habit, reduces specific surface area relatively, and surface can decline, and forms tridimensional network, thereby played pour-point depressing process and be difficult to assemble.
But for plant oil based green, top-grade lubricating oil, common pour point depressant is because relative molecular mass is larger, can with base oil eutectic, even provide the nucleus of condensation to base oil, thereby condensation point raise to some extent.
In the prior art, the main drawback of pour depressant for lubricating oil like product is:
1, most of larger monoesters or polyester of relative molecular mass that adopt.The pour point depressant of monoesters or polyester only has obvious pour-point depressing process for the plain oil of mineral oil based, and for the pour point depression DeGrain of plant oil based green, top-grade lubricating oil.Even make its condensation point slightly raise.
2, most of fossil energy product that adopts.And fossil energy is increasingly exhausted.
Concrete formula is upper, and the pour depressant for lubricating oil generally using in the market, generally has polymethacrylate T602A, polymethacrylate PPT248, polyalphaolefin pour point depressant T803B, polyalphaolefin pour point depressant T803D, T818C etc.
In pour depressant for lubricating oil, adopt rudimentary polynary ester and modification seal to add the report that has no of fruit oil composite type.
Summary of the invention
The object of the invention is to provide for above-mentioned deficiency a kind of and be beneficial to environmental protection, renewable, use range is wider, good stability, the compound pour point depressant of lubricating oil and preparation method that suitability is stronger.
Technical solution of the present invention is: the compound pour point depressant of lubricating oil, made by the component of following volume percent:
Modification prints and adds fruit oil 40%-60%, rudimentary polynary ester 40%-60%.
The weight ratio that described modification seal adds its raw material of fruit oil is: print and add oily 100 parts of fruit, hydrogen peroxide 8-12 part of 1%-3%, lower fatty acid 4-6 part, 45 parts of isooctyl alcohol, 8 parts-50 parts of the vitriol oils.Seal add fruit oily relative molecular mass less, condensation point is lower.
Described rudimentary polynary ester is made up of lower fatty acid and rudimentary multi-alcohol; Its consumption must be strictly according to the metering ratio of chemical reaction; Rudimentary polynary ester is prepared as follows: in enamel reaction still, add successively rudimentary multi-alcohol 50-100Kg and the 50-60L vitriol oil, add 120-264Kg lower fatty acid after mixing, again mix, be slowly heated to boiling; Keep the slight boiling state of reactant, the ester of generation is steamed, by splashing into after condensing tube condensation in the saturated soda ash solution of 50L, in the time no longer including ester generation, stop heating; By product and aqueous phase separation, be washed to the pH=7 of water layer, after being dried, obtain rudimentary polynary ester.
The preparation method of the compound pour point depressant of lubricating oil, is characterized in that step is as follows:
Modification prints the preparation that adds fruit oil:
In enamel reaction still, add 100 parts of seals to add fruit oil, be preheated to 40 DEG C, add successively 4-6 part acetic acid, 1%-3% hydrogen peroxide 8-12 part, the vitriol oil (98%) 8-10 part, stir, maintain the temperature at approximately 40 DEG C, 40min dropwises, and is warming up to 60-65 DEG C, continue the about 2-3h of reaction, obtain epoxidation seal and add the oily product of fruit.Reaction mass is poured out, with 50 parts of massfractions be the pure alkali liquid washing of 0.5%-1% to pH=4, leave standstill after separatory, by separation of oil and dry after obtain epoxidation and print and add fruit oil.
This technique be print add fruit oil first adopt hydrogen peroxide (H
2o
2), acetic acid, catalyzer (98% vitriol oil) carry out epoxidation, and saturated two keys print thereby improved the oxidation-resistance that adds fruit oil.
In enamel reaction still, by weight adding 3 parts of isooctyl alcohol, 2 parts of catalyzer (98% vitriol oil) successively, add epoxidation to print again and add 7 parts of fruit oil after mixing, the 2h-3h that refluxes under the condition of 90 DEG C, carries out esterification, obtains ether-ether.
Under the condition of 70 DEG C-90 DEG C, above-mentioned ether-ether is steamed, after being dried, obtain modification seal and add fruit oil.The benefit of esterification is: greatly strengthened the fat-soluble of pour point depressant, further reduced its condensation point, eliminated the acidity of pour point depressant.
By above-mentioned epoxidation and esterification, not only improve seal and added the oily oxidation-resistance of fruit and fat-soluble, improve again its viscosity index simultaneously, the more important thing is to greatly reduce to print to add the really condensation point of oil.
Test data shows, prints that to add fruit oil viscosity index be 245, and condensation point is-27 DEG C, has certain water-soluble.Modification prints and adds fruit oil viscosity index between 280-350, and condensation point, between-65 DEG C--70 DEG C, is insoluble in water, is soluble in organic solvent.The viscosity-temperature characteristics that this product is good, fat-soluble and anticoagulation are shown.
The preparation of rudimentary polynary ester:
Rudimentary polynary ester is synthetic by lower fatty acid and rudimentary multi-alcohol.Lower fatty acid is acetic acid (molecular formula C
2h
4o
2), propionic acid (C
3h
6o
2) or butyric acid (C
4h
8o
2); Rudimentary multi-alcohol is ethylene glycol (C
2h
6o
2), 1,2-PD (C
3h
8o
2), 1,3-PD (C
3h
8o
2), glycerol (C
3h
8o
3), 1,2-butyleneglycol (C
4h
10o
2), 1,3 butylene glycol (C
4h
10o
2), BDO (C
4h
10o
2) or 2,3-butanediol (C
4h
10o
2).
3. in enamel reaction still, add a certain amount of lower polyol and the appropriate vitriol oil, after mixing, add with lower polyol chemical reaction and measure suitable lower fatty acid, again mix, be slowly heated to boiling.Keep the slight boiling state of reactant, the rudimentary polynary ester generating is steamed, by splashing into after condensing tube condensation in appropriate saturated soda ash solution, in the time no longer including ester generation, stop heating.By product and aqueous phase separation, be washed to the pH=7 of water layer, after being dried, obtain the rudimentary polynary ester with fabulous pour-point depressing process.
Chemical principle:
HO—CH
2—R
1—CH
2—OH + 2R
2COOH →
R
2COO—CH
2—R
1—CH
2—OOCR
2 + 2 H
2O
Modification is printed and adds fruit oil and be about by volume 4:6-6:4 with rudimentary dibasic ester be uniformly mixed and obtain the compound pour point depressant of high performance lubricating oil under 40 DEG C of-50 DEG C of conditions.
Table 1-prints the chemical composition that adds fruit oil
Table 1
Chemical composition |
Molecular formula |
Content/% |
Tetradecanoic acid(tetradecanoic acid) |
C
14H
28O
2 |
0.06 |
Hexadecanoic acid(palmitinic acid) |
C
16H
32O
2 |
10.89 |
Hexadecanoic acid, 15-methyl(15-methyl palmitic acid) |
C
14H
28O
2 |
0.15 |
9,12 ,-Octadecadienoic acid (Z, Z)-(9Z, 12Z-linolic acid) |
C
18H
32O
2 |
34.19 |
Linolenic acid (linolenic acid) |
C
18H
30O
2 |
46.38 |
Stearic acid (stearic acid) |
C
18H
36O
2 |
7.60 |
9,12,15-Octadecadienoic acid (E, E)-(9E, 12E-linolic acid) |
C
18H
32O
2 |
0.09 |
Methyl linolenic acid (methyl linolenic acid) |
C
19H
32O
2 |
0.16 |
9,12,15-Octadecadienoic acid (E, E, E)-(gamma-linolenic acid) |
C
18H
30O
2 |
0.10 |
Cis-11-Eicosenoic acid (cis-11-eicosenoic acid) |
C
20H
38O
2 |
0.26 |
18-methylnonadecanoic acid (18-methyl nondecylic acid) |
C
19H
40O
2 |
0.12 |
Advantage of the present invention is: 1, adopt modification to print and add fruit oil, viscosity is larger, and lubricity is good, and condensation point low (38.8--50.5 DEG C, pour point depression effect is remarkable) is renewable, biodegradable, environmental protection.2, adopt rudimentary polynary ester, raw materials cost is low, and preparation technology is simple, and condensation point is low, and pour point depression is effective.3, there is dual pour-point depressing process.Add fruit oil and rudimentary polynary ester all has very low condensation point because modification prints, after the two is compound, pour point depression effect is remarkable.
Below in conjunction with embodiment, embodiments of the present invention are described in further detail.
Embodiment
Embodiment 1
1. modification prints the preparation that adds fruit oil:
In a there-necked flask, add the seal of 100 parts to add fruit oil, the separating funnel that 5 parts of acetic acid, 10 parts and the 9 parts vitriol oils of 2% hydrogen peroxide are housed is inserted in bottleneck one end, be preheated to 40 DEG C, stir, maintain the temperature at approximately 40 DEG C, 40min dropwises, and is warming up to 62 DEG C, continue the about 2.5h of reaction, obtain epoxidation seal and add the oily product of fruit.Reaction mass is poured out, is placed in separating funnel, with massfraction be 0.8% pure alkali liquid washing to pH=4, leave standstill after separatory, obtain epoxidation after oil phase is dry and print and add fruit oil.
This technique be print add fruit oil first adopt 2% hydrogen peroxide (H
2o
2), acetic acid, catalyzer (98% vitriol oil) carry out epoxidation, and saturated two keys print thereby improved the oxidation-resistance that adds fruit oil.
Then the isooctyl alcohol that adopts long-chain participates in lower and epoxidation at catalyzer (98% vitriol oil) and prints and add really oil and carry out esterification, obtains ether-ether.
In there-necked flask, by weight adding 3 parts of isooctyl alcohol, 2 parts of catalyzer (98% vitriol oil) successively, add epoxidation to print again and add 7 parts of fruit oil after mixing, the 3h that refluxes under the condition of 90 DEG C, carries out esterification, obtains ether-ether.
In the water-bath of 70 DEG C-90 DEG C, above-mentioned ether-ether is steamed, after being dried, obtain modification seal and add fruit oil.
2. the preparation of rudimentary polynary ester:
The zeolite, 50g ethylene glycol and the 30mL vitriol oil that in distilling flask, add 3-5 grain mung bean size, add 100g acetic acid after mixing, again mix, and is slowly heated to boiling.Keep the slight boiling state of reactant, the ethylene diacetate of generation is steamed, by splashing into after condensing tube condensation in the saturated soda ash solution of 50mL, in the time no longer including ester generation, stop heating.By product and aqueous phase separation, be washed to the pH=7 of water layer, after being dried, obtain the rudimentary dibasic ester with fabulous pour-point depressing process.
Chemical principle:
HO—CH
2—CH
2—OH + 2CH
3COOH →
CH
3COO—CH
2—CH
2—OOCCH
3 + 2 H
2O
3. modification seal is added to fruit oil and be uniformly mixed and obtain the compound pour point depressant of high performance lubricating oil for 1:1 low speed under 45 DEG C of conditions by volume with rudimentary dibasic ester.
L-HV 32 low temperature antiwear hydraulic oils are added after the compound pour point depressant of 0.6% lubricating oil, stir at normal temperatures, physical and chemical index changes as shown in table 2.
Table 2
Project |
Add before agent |
Add after agent |
Test method |
Kinematic viscosity mm
2/s 40℃
|
30.87 |
30.55 |
GB/T265 |
Viscosity index |
141 |
139 |
GB/T2541 |
Flash-point (opening) DEG C |
199 |
198 |
GB/T3536 |
Condensation point DEG C |
-35 |
-50.5 |
GB/T3535 |
54 DEG C of demulsibility (40-37-3) min |
10 |
9 |
GB/T7305 |
Embodiment 2
1. modification prints the preparation that adds fruit oil:
In enamel reaction still, add 100Kg to print and add fruit oil, be preheated to 40 DEG C, add successively 4Kg acetic acid, 1.5% hydrogen peroxide 12Kg, the 10Kg vitriol oil (98%), stir, maintain the temperature at approximately 40 DEG C, 40min dropwises, and is warming up to 60 DEG C, continue the about 3h of reaction, obtain epoxidation seal and add the oily product of fruit.Reaction mass is poured out, with massfraction be 0.7% pure alkali liquid washing to pH=4, leave standstill after separatory, by separation of oil and dry after obtain epoxidation and print and add fruit oil.
Then the isooctyl alcohol that adopts long-chain participates in lower and epoxidation at catalyzer (98% vitriol oil) and prints and add really oil and carry out esterification, obtains ether-ether.
In enamel reaction still, by weight adding isooctyl alcohol 30Kg, catalyzer (98% vitriol oil) 20Kg successively, add epoxidation to print again and add the oily 70Kg of fruit after mixing, the 3h that refluxes under the condition of 90 DEG C, carries out esterification, obtains ether-ether.
In the water-bath of 70 DEG C-90 DEG C, above-mentioned ether-ether is steamed, after being dried, obtain modification seal and add fruit oil.
2. the preparation of rudimentary polynary ester:
In enamel reaction still, add 76Kg1, ammediol and the 50L vitriol oil, add 120Kg acetic acid after mixing, again mix, and is slowly heated to boiling.
Keep the slight boiling state of reactant, the diacetate of generation is steamed, by splashing into after condensing tube condensation in the saturated soda ash solution of 50L, in the time no longer including ester generation, stop heating.
By product and aqueous phase separation, be washed to the pH=7 of water layer, after being dried, obtain the rudimentary dibasic ester with fabulous pour-point depressing process.
Chemical principle:
HO—CH
2—CH
2—CH
2—OH + 2CH
3COOH →
CH
3COO—CH
2—CH
2—CH
2—OOCCH
3 + 2H
2O
3. modification seal is added to fruit oil and be uniformly mixed and obtain the compound pour point depressant of lubricating oil for 6:4 low speed under 45 DEG C of conditions by volume with rudimentary dibasic ester.
The Industrial Closed gear oil of loading in CKC-220 is added after 0.5% compound pour point depressant, stir at normal temperatures, physical and chemical index changes as shown in table 3.
Table 3
Project |
Add before agent |
Add after agent |
Test method |
Kinematic viscosity mm
2/s 40℃
|
222.1 |
221.5 |
GB/T265 |
Flash-point (opening) DEG C |
243 |
241 |
GB/T267 |
Condensation point DEG C |
-22 |
-38.5 |
GB/T3535 |
Embodiment 3
Modification prints the preparation that adds fruit oil:
1. in enamel reaction still, add 100 parts of seals to add fruit oil, be preheated to 40 DEG C, add successively 6 parts of acetic acid, 8 parts, the 9 parts vitriol oils of 3% hydrogen peroxide (98%), stir, maintain the temperature at approximately 40 DEG C, 40min dropwises, and is warming up to 64 DEG C, continue the about 3h of reaction, obtain epoxidation seal and add the oily product of fruit.Reaction mass is poured out, with massfraction be 1% pure alkali liquid washing to pH=4, leave standstill after separatory, by separation of oil and dry after obtain epoxidation and print and add fruit oil.
2. the isooctyl alcohol that then adopts long-chain participates in lower and epoxidation at catalyzer (98% vitriol oil) and prints and add really oil and carry out esterification, obtains ether-ether.
In enamel reaction still, by weight adding 3 parts of isooctyl alcohol, 2 parts of catalyzer (98% vitriol oil) successively, add epoxidation to print again and add 7 parts of fruit oil after mixing, the 3h that refluxes under the condition of 90 DEG C, carries out esterification, obtains ether-ether.
In the water-bath of 70 DEG C-90 DEG C, above-mentioned ether-ether is steamed, after being dried, obtain modification seal and add fruit oil.
The preparation of rudimentary polynary ester:
In enamel reaction still, add 90Kg1,4-butyleneglycol and the 60L vitriol oil, add 148Kg propionic acid after mixing, again mix, and is slowly heated to boiling.
Keep the slight boiling state of reactant, the BDO dipropionate of generation is steamed, by splashing into after condensing tube condensation in the saturated soda ash solution of 50L, in the time no longer including ester generation, stop heating.
By product and aqueous phase separation, be washed to the pH=7 of water layer, after being dried, obtain the rudimentary dibasic ester with fabulous pour-point depressing process.
Chemical principle:
HO—CH
2—CH
2—CH
2—CH
2—OH + 2CH
3—CH
2—COOH →
CH
3 —CH
2—COO—CH
2—CH
2—CH
2—CH
2—OOC— CH
2—CH
3 +
2H
2O
Modification seal is added to fruit oil and be uniformly mixed and obtain the compound pour point depressant of lubricating oil for 6:4 low speed under 45 DEG C of conditions by volume with rudimentary dibasic ester.
The Industrial Closed gear oil of loading in CKC-220 is added after 0.5% compound pour point depressant, stir at normal temperatures, physical and chemical index changes as shown in table 4.
Table 4
Project |
Add before agent |
Add after agent |
Test method |
Kinematic viscosity mm
2/s 40℃
|
222.1 |
221.5 |
GB/T265 |
Flash-point (opening) DEG C |
243 |
242 |
GB/T267 |
Condensation point DEG C |
-22 |
-37.5 |
GB/T3535 |
The castor oil-base hydraulic efficiency oil of Tonghua seven-star lubricating oil being manufactured to limited liability company's production adds after 0.6% compound pour point depressant, stirs at normal temperatures, and physical and chemical index changes as shown in table 5.
Table 5
Project |
Add before agent |
Add after agent |
Test method |
Viscosity index |
140 |
139 |
GB/T1995 |
Flash-point (opening) DEG C |
223 |
222 |
GB/T3536 |
Condensation point DEG C |
-32 |
-48.5 |
GB/T3535 |
Embodiment 4
1. modification prints the preparation that adds fruit oil
In enamel reaction still, add 100 parts of seals to add fruit oil, be preheated to 40 DEG C, add successively 5 parts of acetic acid, 12 parts, the 10 parts vitriol oils of 1% hydrogen peroxide (98%), stir, maintain the temperature at approximately 40 DEG C, 40min dropwises, and is warming up to 65 DEG C, continue reaction 2.5h, obtain epoxidation seal and add the oily product of fruit.Reaction mass is poured out, with massfraction be the pure alkali liquid washing of 0.5-1% to pH=4, leave standstill after separatory, by separation of oil and dry after obtain epoxidation and print and add fruit oil.
2. the isooctyl alcohol that then adopts long-chain participates in lower and epoxidation at catalyzer (98% vitriol oil) and prints and add really oil and carry out esterification, obtains ether-ether.
In enamel reaction still, by weight adding 3 parts of isooctyl alcohol, 2 parts of catalyzer (98% vitriol oil) successively, add epoxidation to print again and add 7 parts of fruit oil after mixing, the 3h that refluxes under the condition of 90 DEG C, carries out esterification, obtains ether-ether.
In the water-bath of 70 DEG C-90 DEG C, above-mentioned ether-ether is steamed, after being dried, obtain modification seal and add fruit oil.
The preparation of rudimentary polynary ester
In enamel reaction still, add 92Kg glycerol and the 60L vitriol oil, after mixing, add 264Kg butyric acid, again mix, be slowly heated to boiling.
Keep the slight boiling state of reactant, the BDO dipropionate of generation is steamed, by splashing into after condensing tube condensation in the saturated soda ash solution of 50L, in the time no longer including ester generation, stop heating.
By product and aqueous phase separation, be washed to the pH=7 of water layer, after being dried, obtain the rudimentary ternary ester with fabulous pour-point depressing process.
Chemical principle:
C
3H
5(OH)
3 + 3C
3H
7—COOH →
(C
3H
7—COO)
3 C
3H
5 + 3H
2O
Modification seal is added to fruit oil and be uniformly mixed and obtain the compound pour point depressant of lubricating oil for 6:4 low speed under 45 DEG C of conditions by volume with rudimentary ternary ester.
The Industrial Closed gear oil of loading in CKC-220 is added after 0.4% compound pour point depressant, stir at normal temperatures, physical and chemical index changes as shown in table 6.
Table 6
Project |
Add before agent |
Add after agent |
Test method |
Kinematic viscosity mm
2/s 40℃
|
222.1 |
221.5 |
GB/T265 |
Flash-point (opening) DEG C |
243 |
242 |
GB/T267 |
Condensation point DEG C |
-22 |
-37.5 |
GB/T3535 |
The castor oil-base hydraulic efficiency oil of Tonghua seven-star lubricating oil being manufactured to limited liability company's production adds after 0.6% compound pour point depressant, stirs at normal temperatures, and physical and chemical index changes as shown in table 7.
Table 7
Project |
Add before agent |
Add after agent |
Test method |
Viscosity index |
140 |
139 |
GB/T1995 |
Flash-point (opening) DEG C |
223 |
222 |
GB/T3536 |
Condensation point DEG C |
-32 |
-49.5 |
GB/T3535 |
Conclusion
Compound pour point depressant synthesis technique is simple, better for the pour point depression effect of plant oil based top-grade lubricating oil.