Lubricating oil compound pour point depressant and preparation method
technical field
The present invention relates to a kind of lubricating oil additive, i.e. lubricating oil compound pour point depressant and preparation method.Trade name: bar figure board 2014 type pour depressant for lubricating oil.
Background technology
The depression mechanism of pour depressant for lubricating oil: well-known, about depression mechanism, mainly also exists nucleation theory and theoretical two kinds of eutectic.The pour-point depressing process of eutectic theoretical explanation dibehenyl fumarate-vinyl acetate copolymer to naphthenic lube oil is more reasonable.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, when growing up to about 200 μm, connects to net, destroys the mobility of oil product.After adding 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, instead of nucleus original in lattice and there occurs eutectic.But because the polar portion in T818C pour point depressant molecule is to solidify in crystal molecule different, hinder the growth of crystallization in X, Y direction, but the crystallization speed of growth in the Z-axis direction is relatively accelerated, have also been changed the shape of crystallization simultaneously, make crystal gradually towards the ingotism future development that branch is many.After T818C pour point depressant adds, while promotion crystallization grows to Z-direction, inhibit the growth to X, Y direction, crystal formation is changed to rectangular pyramid, four prism type by irregular bulk.This crystal habit, makes specific surface area relatively reduce, and surface energy declines, and is difficult to assemble formation tridimensional network, thus serves pour-point depressing process.
But, for plant oil based green, top-grade lubricating oil, common pour point depressant due to relative molecular mass comparatively large, then can with base oil eutectic, even provide the nucleus of condensation to base oil, thus condensation point raised to some extent.
In the prior art, the main drawback of pour depressant for lubricating oil like product is:
1, major part adopts the monoesters or polyester that relative molecular mass is larger.The pour point depressant of monoesters or polyester only has obvious pour-point depressing process for the plain oil of mineral oil based, and not obvious for the depression effeCt of plant oil based green, top-grade lubricating oil.Its condensation point is even made slightly to raise.
2, major part adopts fossil energy product.And fossil energy is increasingly exhausted.
On concrete formula, the pour depressant for lubricating oil generally used in the market, generally has polymethacrylate T602A, polymethacrylate PPT248, polyalphaolefin pour point depressant T803B, polyalphaolefin pour point depressant T803D, T818C etc.
What adopt lower polyhydric ester and modification to print to add fruit oil composite type in pour depressant for lubricating oil has no report.
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, the lubricating oil compound pour point depressant that renewable, use range is wider, good stability, suitability are stronger and preparation method.
Technical solution of the present invention is: lubricating oil compound pour point depressant, is made up of the component of following volume percent:
Modification print adds fruit oil 40%-60%, lower polyhydric ester 40%-60%.
The weight ratio that described modification print adds its raw material of fruit oil is: print adds fruit oil 100 parts, hydrogen peroxide 8-12 part of 1%-3%, lower fatty acid 4-6 part, isooctyl alcohol 45 parts, the vitriol oil 8 parts-50 parts.Print add fruit oily relative molecular mass less, condensation point is lower.
Described lower polyhydric ester is made up of lower fatty acid and lower polyhydric fatty alcohol; Its consumption must strictly according to the metering ratio of chemical reaction; Lower polyhydric ester is prepared as follows: in enamel reaction still, add lower polyhydric fatty alcohol 50-100Kg and the 50-60L vitriol oil successively, add 120-264Kg lower fatty acid, again mix after mixing, and is slowly heated to boiling; Keeping the slight boiling state of reactant, the ester of generation is steamed, by instilling in the saturated soda ash solution of 50L after condensing tube condensation, when no longer including ester and generating, stopping heating; By product and aqueous phase separation, be washed to the pH=7 of water layer, after drying, namely obtain lower polyhydric ester.
The preparation method of lubricating oil compound pour point depressant, is characterized in that step is as follows:
Modification print adds the preparation of fruit oil:
In enamel reaction still, add 100 parts of prints add fruit oil, be preheated to 40 DEG C, add 4-6 part acetic acid, 1%-3% hydrogen peroxide 8-12 part, the vitriol oil (98%) 8-10 part successively, stir, maintain the temperature at about 40 DEG C, 40min dropwises, and is warming up to 60-65 DEG C, continue to react about 2-3h, obtain epoxidation print 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, namely separation of oil is obtained epoxidation print and add fruit oil after drying.
This technique be print add fruit oil first adopt hydrogen peroxide (H
2o
2), acetic acid, catalyzer (98% vitriol oil) carry out epoxidation, are saturated double bond, thus improve the oxidation-resistance printing and add fruit oil.
By weight adding isooctyl alcohol 3 parts, catalyzer (98% vitriol oil) 2 parts successively in enamel reaction still, add epoxidation print after mixing again and add fruit oil 7 parts, reflux 2h-3h under the condition of 90 DEG C, carries out esterification, obtain ether-ether.
Under the condition of 70 DEG C-90 DEG C, above-mentioned ether-ether is steamed, namely obtain modification print after drying and add fruit oil.The benefit of esterification is: greatly strengthen the fat-soluble of pour point depressant, reduce further its condensation point, eliminates the acidity of pour point depressant.
By above-mentioned epoxidation and esterification, not only increase the oxidation-resistance and fat-soluble that print adds fruit oil, turn improve its viscosity index simultaneously, the more important thing is the condensation point greatly reducing print and add fruit oil.
Test data shows, it is 245 that print adds fruit oil viscosity index, and condensation point is-27 DEG C, has certain water-soluble.Modification print adds fruit oil viscosity index between 280-350, and condensation point is at-65 DEG C--and between 70 DEG C, be insoluble in water, be soluble in organic solvent.Show the excellent viscosity-temperature characteristics of this product, fat-soluble and anticoagulation.
The preparation of lower polyhydric ester:
Lower polyhydric ester is synthesized by lower fatty acid and lower polyhydric fatty 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); Lower polyhydric fatty 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, add after mixing and measure suitable lower fatty acid with lower polyol chemical reaction, again mix, be slowly heated to boiling.Keeping the slight boiling state of reactant, the lower polyhydric ester of generation is steamed, by instilling in appropriate saturated soda ash solution after condensing tube condensation, when no longer including ester and generating, stopping heating.By product and aqueous phase separation, be washed to the pH=7 of water layer, after drying, namely obtain the lower polyhydric 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+2H
2O
Modification print is added fruit oil be about 4:6-6:4 by volume under 40 DEG C of-50 DEG C of conditions, be uniformly mixed and obtain high performance lubricating oil compound pour point depressant with rudimentary dibasic ester.
Table 1-print adds the chemical composition of 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-methyinonadecanoic acid) |
C
19H
40O
2 |
0.12 |
Advantage of the present invention is: 1, adopt modification print to add fruit oil, viscosity is comparatively large, and lubricity is excellent, condensation point low (-38.8--50.5 DEG C, depression effeCt is remarkable), renewable, biodegradable, environmental protection.2, adopt lower polyhydric ester, raw materials cost is low, and preparation technology is simple, and condensation point is low, and depression effeCt is good.3, there is dual pour-point depressing process.All have very low condensation point because modification print adds really oil and lower polyhydric ester, after the two compound, depression effeCt is remarkable.
Below in conjunction with embodiment, embodiments of the present invention are described in further detail.
Embodiment
Embodiment 1
1. modification print adds the preparation of fruit oil:
The print adding 100 parts in a there-necked flask adds fruit oil, the separating funnel that 5 parts of acetic acid, 2% hydrogen peroxide, 10 parts and the 9 parts vitriol oils are housed is inserted in bottleneck one end, be preheated to 40 DEG C, stir, maintain the temperature at about 40 DEG C, 40min dropwises, and is warming up to 62 DEG C, continue to react about 2.5h, obtain epoxidation print 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, leaving standstill after separatory, adding fruit oil by namely obtaining epoxidation print after oil phase drying.
This technique be print add fruit oil first adopt 2% hydrogen peroxide (H
2o
2), acetic acid, catalyzer (98% vitriol oil) carry out epoxidation, are saturated double bond, thus improve the oxidation-resistance printing and add fruit oil.
Then adopt the isooctyl alcohol of long-chain to participate in lower to print with epoxidation at catalyzer (98% vitriol oil) to add really oil and carry out esterification, obtain ether-ether.
By weight adding isooctyl alcohol 3 parts, catalyzer (98% vitriol oil) 2 parts successively in there-necked flask, add epoxidation print after mixing again and add fruit oil 7 parts, reflux 3h under the condition of 90 DEG C, carries out esterification, obtain ether-ether.
In the water-bath of 70 DEG C-90 DEG C, above-mentioned ether-ether is steamed, namely obtain modification print after drying and add fruit oil.
2. the preparation of lower polyhydric ester:
In distilling flask, add the zeolite of 3-5 grain mung bean size, 50g ethylene glycol and the 30mL vitriol oil, add 100g acetic acid after mixing, again mix, be slowly heated to boiling.Keeping the slight boiling state of reactant, the ethylene diacetate of generation is steamed, by instilling in the saturated soda ash solution of 50mL after condensing tube condensation, when no longer including ester and generating, stopping heating.By product and aqueous phase separation, be washed to the pH=7 of water layer, after drying, namely 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+2H
2O
3. modification print is added fruit oil and be uniformly mixed and obtain high performance lubricating oil compound pour point depressant for 1:1 low speed under 45 DEG C of conditions by volume with rudimentary dibasic ester.
After L-HV32 low temperature antiwear hydraulic oil being added 0.6% lubricating oil compound pour point depressant, stir at normal temperatures, physical and chemical mutagenesis is as shown in table 2.
Table 2
Project |
Before adding agent |
After adding 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 |
Demulsibility (40-37-3) min 54 DEG C |
10 |
9 |
GB/T7305 |
Embodiment 2
1. modification print adds the preparation of fruit oil:
In enamel reaction still, add 100Kg print add fruit oil, be preheated to 40 DEG C, add 4Kg acetic acid, 1.5% hydrogen peroxide 12Kg, 10Kg vitriol oil (98%) successively, stir, maintain the temperature at about 40 DEG C, 40min dropwises, and is warming up to 60 DEG C, continue to react about 3h, obtain epoxidation print 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, namely separation of oil is obtained epoxidation print and add fruit oil after drying.
Then adopt the isooctyl alcohol of long-chain to participate in lower to print with epoxidation at catalyzer (98% vitriol oil) to add really oil and carry out esterification, obtain ether-ether.
By weight adding isooctyl alcohol 30Kg, catalyzer (98% vitriol oil) 20Kg successively in enamel reaction still, add epoxidation print after mixing again and add the oily 70Kg of fruit, reflux 3h under the condition of 90 DEG C, carries out esterification, obtain ether-ether.
In the water-bath of 70 DEG C-90 DEG C, above-mentioned ether-ether is steamed, namely obtain modification print after drying and add fruit oil.
2. the preparation of lower polyhydric ester:
In enamel reaction still, add 76Kg1, ammediol and the 50L vitriol oil, add 120Kg acetic acid, again mix after mixing, and is slowly heated to boiling.
Keeping the slight boiling state of reactant, the diacetate of generation is steamed, by instilling in the saturated soda ash solution of 50L after condensing tube condensation, when no longer including ester and generating, stopping heating.
By product and aqueous phase separation, be washed to the pH=7 of water layer, after drying, namely 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 print is added fruit oil and be uniformly mixed and obtain lubricating oil compound pour point depressant for 6:4 low speed under 45 DEG C of conditions by volume with rudimentary dibasic ester.
After in CKC-220, load Industrial Closed gear oil adds 0.5% compound pour point depressant, stir at normal temperatures, physical and chemical mutagenesis is as shown in table 3.
Table 3
Project |
Before adding agent |
After adding 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 print adds the preparation of fruit oil:
1. in enamel reaction still, add 100 parts of prints add fruit oil, be preheated to 40 DEG C, add 6 parts of acetic acid, 3% hydrogen peroxide 8 parts, 9 parts of vitriol oils (98%) successively, stir, maintain the temperature at about 40 DEG C, 40min dropwises, and is warming up to 64 DEG C, continue to react about 3h, obtain epoxidation print 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, namely separation of oil is obtained epoxidation print and add fruit oil after drying.
2. then adopt the isooctyl alcohol of long-chain to participate in lower to print with epoxidation at catalyzer (98% vitriol oil) to add really oil and carry out esterification, obtain ether-ether.
By weight adding isooctyl alcohol 3 parts, catalyzer (98% vitriol oil) 2 parts successively in enamel reaction still, add epoxidation print after mixing again and add fruit oil 7 parts, reflux 3h under the condition of 90 DEG C, carries out esterification, obtain ether-ether.
In the water-bath of 70 DEG C-90 DEG C, above-mentioned ether-ether is steamed, namely obtain modification print after drying and add fruit oil.
The preparation of lower polyhydric ester:
In enamel reaction still, add 90Kg1,4-butyleneglycol and the 60L vitriol oil, add 148Kg propionic acid, again mix after mixing, and is slowly heated to boiling.
Keeping the slight boiling state of reactant, the BDO dipropionate of generation is steamed, by instilling in the saturated soda ash solution of 50L after condensing tube condensation, when no longer including ester and generating, stopping heating.
By product and aqueous phase separation, be washed to the pH=7 of water layer, after drying, namely 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 print is added fruit oil and is uniformly mixed and obtains lubricating oil compound pour point depressant for 6:4 low speed under 45 DEG C of conditions by volume with rudimentary dibasic ester.
After in CKC-220, load Industrial Closed gear oil adds 0.5% compound pour point depressant, stir at normal temperatures, physical and chemical mutagenesis is as shown in table 4.
Table 4
Project |
Before adding agent |
After adding 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 |
After the castor oil-base hydraulic efficiency oil that Tonghua seven-star lubricating oil manufacture limited liability company produces is added 0.6% compound pour point depressant, stir at normal temperatures, physical and chemical mutagenesis is as shown in table 5.
Table 5
Project |
Before adding agent |
After adding 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 print adds the preparation of fruit oil
In enamel reaction still, add 100 parts of prints add fruit oil, be preheated to 40 DEG C, add 5 parts of acetic acid, 1% hydrogen peroxide 12 parts, 10 parts of vitriol oils (98%) successively, stir, maintain the temperature at about 40 DEG C, 40min dropwises, and is warming up to 65 DEG C, continue reaction 2.5h, obtain epoxidation print 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, namely separation of oil is obtained epoxidation print and add fruit oil after drying.
2. then adopt the isooctyl alcohol of long-chain to participate in lower to print with epoxidation at catalyzer (98% vitriol oil) to add really oil and carry out esterification, obtain ether-ether.
By weight adding isooctyl alcohol 3 parts, catalyzer (98% vitriol oil) 2 parts successively in enamel reaction still, add epoxidation print after mixing again and add fruit oil 7 parts, reflux 3h under the condition of 90 DEG C, carries out esterification, obtain ether-ether.
In the water-bath of 70 DEG C-90 DEG C, above-mentioned ether-ether is steamed, namely obtain modification print after drying and add fruit oil.
The preparation of lower polyhydric ester
In enamel reaction still, add 92Kg glycerol and the 60L vitriol oil, add 264Kg butyric acid after mixing, again mix, be slowly heated to boiling.
Keeping the slight boiling state of reactant, the BDO dipropionate of generation is steamed, by instilling in the saturated soda ash solution of 50L after condensing tube condensation, when no longer including ester and generating, stopping heating.
By product and aqueous phase separation, be washed to the pH=7 of water layer, after drying, namely 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)
3C
3H
5+3H
2O
Modification print is added fruit oil and is uniformly mixed and obtains lubricating oil compound pour point depressant for 6:4 low speed under 45 DEG C of conditions by volume with rudimentary ternary ester.
After in CKC-220, load Industrial Closed gear oil adds 0.4% compound pour point depressant, stir at normal temperatures, physical and chemical mutagenesis is as shown in table 6.
Table 6
Project |
Before adding agent |
After adding 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 |
After the castor oil-base hydraulic efficiency oil that Tonghua seven-star lubricating oil manufacture limited liability company produces is added 0.6% compound pour point depressant, stir at normal temperatures, physical and chemical mutagenesis is as shown in table 7.
Table 7
Project |
Before adding agent |
After adding 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, and the depression effeCt for plant oil based top-grade lubricating oil is better.