CN107082849B - A kind of quadripolymer diesel pour inhibitor and preparation method thereof - Google Patents

Abstract

The invention discloses a quaternary polymer diesel pour point depressant and a preparation method thereof. It specifically includes the following steps: (1) taking several kinds of higher alcohols and fumaric acid for esterification reaction to prepare higher alcohol fumaric acid esters; (2) weighing higher alcohol fumaric acid esters, ethylene acetic acid Vinyl ester, dicyclopentadiene and initiator are polymerized in a solvent. After the reaction, ethylenediamine and catalyst are added, and the reaction is continued. Finally, the reaction product is distilled under reduced pressure and washed with alcohol to obtain the tetrapolymer diesel oil depreciation. agent. When the quaternary polymer diesel pour point depressant prepared by the present invention is used in 0# diesel oil, it can be evenly dispersed in diesel oil, effectively improving the low-temperature fluidity of diesel oil. In addition, the preparation method of the present invention is simple, and the raw material price is cheap and easy to obtain. When the addition amount is 0.1%, the cold filter point of 0# diesel can be reduced by 12-19°C, and the condensation point can be reduced by 18-25°C.

Description

A kind of quaternary polymer diesel oil point depressant and preparation method thereof

technical field

The invention specifically relates to a quaternary polymer diesel pour point depressant and a preparation method thereof, belonging to the technical field of biomass energy additives.

Background technique

In industries such as energy and transportation, diesel oil occupies a very important position, especially 0# diesel oil accounts for more than 70% of the total amount of diesel oil, especially in northern my country and some cold regions, low temperature will cause diesel oil to crystallize and block the engine oil pipeline With the filter, the affected engine does not work properly.

A pour point depressant (called a low temperature flow improver) is a chemically polymerized compound that can lower the freezing point or cold filter point of oil. Due to the poor low-temperature fluidity of diesel oil currently used in our country, especially as the temperature continues to decrease, it leads to the disadvantages of diesel crystallization and poor low-temperature fluidity. These diesel oils basically cannot be used under low temperature conditions. In order to overcome the above shortcomings, enhance the low temperature fluidity of the oil, and further expand the scope of use of the oil, the oil is usually treated with a dewaxing process to improve its low temperature fluidity. However, for the dewaxing process, in order to obtain a lower freezing point for the oil, it is usually necessary to continuously reduce the temperature of the dewaxing process, which will increase energy consumption and increase costs. In order to solve the above problems, Achieving deep pour point depressing is generally achieved by adding pour point depressant to the oil.

The polymer pour point depressants commonly used in the market mainly include ethylene-vinyl acetate copolymer, maleic anhydride copolymer, vinyl acetate-fumarate copolymer, alkenyl diamic acid salts, alkyl aromatic hydrocarbons, acrylic acid Ester copolymers and polar nitrogen-containing compounds, etc. Although there are many types of pour point depressants, a single component cannot satisfy complex diesel oils. Therefore, a multi-component, multifunctional, multi-polymer polymer pour point depressant suitable for most diesel oils is needed to improve the low temperature flow properties of diesel oil.

Contents of the invention

One of the purposes of the present invention is to improve the general applicability of the single polymer pour point depressant, enhance its pour point depressant effect, and gain a new understanding of the crystallization behavior of diesel wax crystals.

The second object of the present invention is to provide a method for preparing the above-mentioned tetrapolymer diesel pour point depressant, so as to make the development of the pour point depressant more diversified.

The technical solution of the present invention is specifically introduced as follows.

The present invention provides a kind of preparation method of quaternary polymer diesel oil point depressant, and concrete steps are as follows:

(1) After mixing several kinds of high-carbon alcohols, carry out esterification reaction with fumaric acid to obtain fumaric acid high-carbon mixed alcohol esters; wherein: the high-carbon alcohols are composed of lauryl alcohol, tetradecyl alcohol, cetyl alcohol Composed of alcohol and stearyl alcohol, lauryl alcohol, tetradecyl alcohol, cetyl alcohol, stearyl alcohol are weighed according to the ratio of 1:1:1:1, 1:2:2:2 or 1:3:3:1;

(2) Polymerize fumaric acid high-carbon mixed alcohol ester, ethylene vinyl acetate, and dicyclopentadiene under the action of an initiator in a solvent, and then add ethylenediamine and a catalyst to the reaction system to continue amine chemical reaction to obtain fumarate high-carbon mixed alcohol ester-ethylene vinyl acetate-dicyclopentadiene-ethylenediamine tetrapolymer, that is, tetrapolymer diesel pour point depressant; among them, fumaric acid high-carbon mixed The molar ratio of alcohol ester, ethylene vinyl acetate and dicyclopentadiene is 3:(1.5-4):(0.5-2); the molar ratio of ethylenediamine to dicyclopentadiene is 1:1.

In the present invention, in step (1), the esterification reaction temperature is 110-160° C., and the reaction time is 4-5 hours.

In the present invention, in step (1), in the esterification reaction, p-toluenesulfonic acid is used as a catalyst, and its consumption is 1%-1.5% of the total mass of several high-carbon alcohols and fumaric acid; agent, the polymerization inhibitor is hydroquinone, and its consumption is 0.6%-1% of the total mass of several high-carbon alcohols and fumaric acid.

Among the present invention, in step (2), solvent is toluene, and initiator is benzoyl peroxide; Its consumption is the 1%-1% of fumaric acid higher carbon mixed alcohol ester, ethylene vinyl acetate and dicyclopentadiene gross mass. 1.5%;

In the present invention, in step (2), the polymerization reaction temperature is 90°C-110°C, and the reaction time is 5-6h.

In the present invention, in step (2), during the amination reaction, the catalyst added is p-toluenesulfonic acid, and its consumption is the total amount of fumaric acid high-carbon mixed alcohol ester, ethylene vinyl acetate, dicyclopentadiene and ethylenediamine. 1.3%-1.7% of the mass; the amination reaction temperature is 100°C-110°C, and the reaction time is 13-16h.

The present invention also provides a tetrapolymer pour point depressant obtained by the above-mentioned preparation method.

Compared with the prior art, the beneficial effects of the present invention are:

A quaternary polymer pour point depressant of the present invention, wherein the four monomeric polymers of fumaric acid high-carbon mixed alcohol ester, ethylene vinyl acetate, dicyclopentadiene and ethylenediamine have a certain pour point depressant effect , but the broad spectrum is not good, which is not conducive to the promotion of the market. Now it is polymerized to form a tetrapolymer to better enhance its pour point depressing effect. It is suitable for diesel oil in many regions. It has strong broad spectrum and good oil solubility. Both play a depressant effect together, so the low temperature fluidity of diesel oil is further improved. Applying the quaternary polymer pour point depressant of the present invention to 0# diesel oil can reduce the filter point and condensation point of 0# diesel oil by 12-19°C and 18-25°C respectively.

Detailed ways

The technical solutions of the present invention will be further described below in conjunction with specific examples, but the present invention is not limited to the following examples.

The measurement method of the freezing point in the present invention is carried out according to "GB510-83 Determination of the freezing point of petroleum products", and the measurement method of the cold filter point is carried out according to "SH/T0248-2006 Diesel and civil heating oil cold filter point measurement method".

Example 1

A kind of quaternary polymer pour point depressant, it is prepared by the method comprising the following steps:

(1) Synthesis of high-carbon mixed alcohol fumaric acid ester: take high-carbon mixed alcohol, catalyst pair The consumption of toluenesulfonic acid is 1% of high carbon mixed alcohol and fumaric acid gross mass, and the consumption of inhibitor hydroquinone is 0.6% of high carbon mixed alcohol and fumaric acid gross mass and solvent toluene joins In the three-necked flask of the condenser, the water separator, and the magnetic stirring device, magnetic heating and stirring are carried out at 55° C. to fully dissolve the raw materials, and then a certain amount of fumaric acid is added to the reactor (the molar ratio of high-carbon mixed alcohol to fumaric acid is 1:1.5), after the reaction at 110°C for 4h, the product was distilled under reduced pressure to remove toluene at 55°C, and then washed the crude ester with 5%, 60°C NaOH solution to remove excess p-toluenesulfonic acid and fumaric acid until liquid It is weakly alkaline, washed in hot distilled water at 80°C to neutral water, and dried in vacuum at 60°C for 5 hours to prepare high-carbon mixed alcohol fumarate;

(2) Synthesis of fumarate high-carbon mixed alcohol ester-ethylene vinyl acetate-dicyclopentadiene aminated compound: first weigh a certain quality of fumaric acid high-carbon mixed alcohol ester, ethylene vinyl acetate, dicyclopentadiene Diene (fumaric acid high-carbon mixed alcohol ester: ethylene vinyl acetate: dicyclopentadiene=3:1.5:0.5), the amount of initiator benzoyl peroxide is fumaric acid high-carbon mixed alcohol ester, ethylene acetic acid 1% of the total mass of vinyl ester and dicyclopentadiene, and solvent toluene were added to a four-necked flask equipped with an electric stirrer, a thermostat, a constant pressure dropping funnel, a reflux condenser tube, and a nitrogen inlet tube, and heated by magnetic force at 60 ° C. Stir and dissolve evenly, react at 90°C for 5 hours, and then add ethylenediamine (the molar ratio of ethylenediamine to dicyclopentadiene is 1:1) and catalyst toluenesulfonic acid into the four-necked flask. 1.3% of the total mass of high-carbon mixed alcohol esters, ethylene vinyl acetate, dicyclopentadiene and ethylenediamine, reacted at 100°C for 13 hours, distilled the reaction product under reduced pressure to remove the solvent, washed with toluene and methanol for 4-5 times, and obtained white After the precipitation, it was washed with toluene and dried under vacuum at 60°C for 48 hours to obtain a white product, that is, fumarate high carbon mixed alcohol ester-ethylene vinyl acetate-dicyclopentadiene-ethylenediamine tetrapolymer.

The quaternary polymer pour point depressant obtained by the above preparation method is preferably added at a mass ratio of 0.1%, added to 0# diesel, and ultrasonically dispersed at 55°C for 30 minutes. Compared with 0# diesel, it is 0# diesel. The cold filter point is lowered by 12°C, and the condensation point is lowered by 18°C.

Example 2

The difference from Example 1 is that the high-carbon mixed alcohol used in the preparation step (1) of the tetrapolymer pour point depressant is according to lauryl alcohol: tetradecyl alcohol: cetyl alcohol: stearyl alcohol=1:2: The ratio of 2:2 is weighed, the amount of catalyst p-toluenesulfonic acid is 1.2% of the total mass of high-carbon mixed alcohol and fumaric acid, and the consumption of polymerization inhibitor hydroquinone is the total mass of high-carbon mixed alcohol and fumaric acid. 0.8% of the mass, after the esterification reaction is completed at 120°C for 4.5 hours;

The mol ratio of used fumaric acid high carbon mixed alcohol ester, ethylene vinyl acetate, dicyclopentadiene in step (2) is 3:2.5:1.5, and the amount of used initiator benzoyl peroxide is fumaric acid high carbon 1.2% of the total mass of mixed alcohol esters, ethylene vinyl acetate and dicyclopentadiene, the amount of catalyst p-toluenesulfonic acid is the total 1.5% by mass, the polymerization temperature of high-carbon mixed alcohol fumarate, ethylene vinyl acetate and dicyclopentadiene is 100°C, the reaction time is 5.5h, and the amination reaction is 14.5h at 110°C.

Others are the same as in Example 1.

The quaternary polymer pour point depressant obtained by the above preparation method is preferably added at a mass ratio of 0.1%, added to 0# diesel, and ultrasonically dispersed at 55°C for 30 minutes. Compared with 0# diesel, it is 0# diesel. The cold filter point decreased by 16°C, and the condensation point decreased by 23°C.

Example 3

The difference from Example 1 is that the high-carbon mixed alcohol used in the preparation step (1) of the tetrapolymer pour point depressant is according to lauryl alcohol: tetradecyl alcohol: cetyl alcohol: stearyl alcohol=1:3: The ratio of 3:1 is weighed, the amount of catalyst p-toluenesulfonic acid is 1.5% of the total mass of high-carbon mixed alcohol and fumaric acid, and the consumption of polymerization inhibitor hydroquinone is the total mass of high-carbon mixed alcohol and fumaric acid. 1% of the mass, after the esterification reaction is completed at 125°C for 5 hours;

The mol ratio of used fumaric acid high carbon mixed alcohol ester, ethylene vinyl acetate, dicyclopentadiene in step (2) is 3:4:2, and the amount of used initiator benzoyl peroxide is fumaric acid high carbon 1.5% of the total mass of mixed alcohol esters, ethylene vinyl acetate and dicyclopentadiene, and the amount of catalyst p-toluenesulfonic acid is the total 1.7% by mass, the polymerization temperature of high-carbon mixed alcohol fumarate, ethylene vinyl acetate and dicyclopentadiene is 110°C, the reaction time is 6h, and the amination reaction is 16h at 110°C.

Others are the same as in Example 1.

The quaternary polymer pour point depressant obtained by the above preparation method is preferably added at a mass ratio of 0.1%, added to 0# diesel, and ultrasonically dispersed at 55°C for 30 minutes. Compared with 0# diesel, it is 0# diesel. The cold filter point decreased by 19°C, and the condensation point decreased by 25°C.

Can draw from above-mentioned embodiment 1-3, quaternary polymer pour point depressant has good pour point depressant effect for 0# diesel oil, by changing the experimental condition in the reaction process, the prepared quaternary polymer pour point depressant also It has different effects, which may be due to the thoroughness of the reaction in the reaction process and the content of different high-carbon alcohols in mixed alcohol esters. Due to the different carbon chain lengths of high-carbon alcohols, there are also obvious differences in the pour point depressing effect of diesel oil. In addition, the amount of catalyst, polymerization inhibitor, initiator and molar ratio of reactants used in the synthesis of tetrapolymer are also factors that restrict the effect of pour point depressing.

In summary, a tetrapolymer pour point depressant of the present invention has a strong sensitivity to diesel paraffin molecules. The individual monomers of the quaternary polymer work together to improve the low temperature fluidity of diesel.

The above content is only a basic description of the concept of the present invention, and any equivalent transformation made according to the technical solution of the present invention shall belong to the protection scope of the present invention.

Claims (7)

1. a preparation method of quaternary polymer diesel oil pour point depressant, is characterized in that, concrete steps are as follows: (1) After mixing several kinds of high-carbon alcohols, carry out esterification reaction with fumaric acid to obtain fumaric acid high-carbon mixed alcohol esters; wherein: the high-carbon alcohols are composed of lauryl alcohol, tetradecyl alcohol, cetyl alcohol Composed of alcohol and stearyl alcohol, lauryl alcohol, tetradecyl alcohol, cetyl alcohol, stearyl alcohol are weighed according to the ratio of 1:1:1:1, 1:2:2:2 or 1:3:3:1; (2) Polymerize fumaric acid high-carbon mixed alcohol ester, ethylene vinyl acetate, and dicyclopentadiene under the action of an initiator in a solvent, and then add ethylenediamine and a catalyst to the reaction system to continue amine chemical reaction to obtain fumarate high-carbon mixed alcohol ester-ethylene vinyl acetate-dicyclopentadiene-ethylenediamine tetrapolymer, that is, tetrapolymer diesel pour point depressant; among them, fumaric acid high-carbon mixed The molar ratio of alcohol ester, ethylene vinyl acetate and dicyclopentadiene is 3:(1.5-4):(0.5-2); the molar ratio of ethylenediamine to dicyclopentadiene is 1:1. 2. The preparation method according to claim 1, characterized in that, in step (1), the esterification reaction temperature is 110-160° C., and the reaction time is 4-5 hours. 3. preparation method according to claim 1 is characterized in that, step (1), in the esterification reaction, adopts p-toluenesulfonic acid as catalyst, and its consumption is 1% of several kinds of higher carbon alcohols and fumaric acid gross mass %-1.5%; In the esterification reaction, add a polymerization inhibitor, the polymerization inhibitor is hydroquinone, and its consumption is 0.6%-1% of the total mass of several high-carbon alcohols and fumaric acid. 4. preparation method according to claim 1 is characterized in that, in step (2), solvent is toluene, and initiator is benzoyl peroxide; Its consumption is fumaric acid higher carbon mixed alcohol ester, ethylene vinyl acetate 1%-1.5% of the total mass of ester and dicyclopentadiene. 5. The preparation method according to claim 1, characterized in that, in step (2), the polymerization reaction temperature is 90°C-110°C, and the reaction time is 5-6h. 6. preparation method according to claim 1 is characterized in that, in step (2), during amination reaction, the catalyzer that adds is p-toluenesulfonic acid, and its consumption is fumaric acid higher carbon mixed alcohol ester, ethylene acetic acid 1.3%-1.7% of the total mass of vinyl ester, dicyclopentadiene and ethylenediamine; the amination reaction temperature is 100°C-110°C, and the reaction time is 13-16h. 7. A tetrapolymer diesel pour point depressant obtained according to the preparation method described in any one of claims 1-6.