CN115651122B - Pour point depressant, preparation method and application thereof - Google Patents
Pour point depressant, preparation method and application thereof Download PDFInfo
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Abstract
The application discloses a pour point depressant, a preparation method and application thereof, and belongs to the technical field of pour point depressants for crude oil. The preparation method of the pour point depressant comprises the following steps: (1) the molar ratio is (20-30): (10-15): polymerizing fumaric acid, caffeic acid and indole monomers in the formula (5-10) to obtain an intermediate A; (2) Reacting the intermediate A in the step (1) with a ketone monomer to obtain an intermediate B; (3) And esterifying and/or amidating the intermediate B and the functional monomer to obtain the pour point depressant. The pour point depressant is prepared by polymerizing maleic acid, caffeic acid and indole monomers, grafting modification is performed by adopting ketone monomers and functional monomers, the synthesis process is simple, higher pour point depressant and viscosity reduction effect can be obtained, and the pour point depressant also has salt tolerance and acid tolerance of the pour point depressant.
Description
Technical Field
The application relates to a pour point depressant, a preparation method and application thereof, and belongs to the technical field of pour point depressants for crude oil.
Background
Most of crude oil in China belongs to waxy crude oil, wax crystals are gradually precipitated when the temperature of the crude oil is close to a wax precipitation point, and a three-dimensional network structure is formed along with the increase of the number of the wax crystals, so that the fluidity of the crude oil is poor, and the normal exploitation and transportation of the crude oil are affected.
At present, in order to solve the problems of crude oil exploitation and transportation caused by wax crystals, a certain amount of chemical pour point depressant is generally added into crude oil, and the precipitation of the wax crystals in the crude oil can be effectively inhibited through the chemical pour point depressant, so that the wax crystals are prevented from forming a three-dimensional network structure, the fluidity of the crude oil is improved, and the normal exploitation and transportation of the crude oil are ensured.
The existing chemical pour point depressants are various, and some of the development of the chemical pour point depressants also needs to consider the characteristics of crude oil in a mining area, for example, in patent CN113121746a, in order to reduce the influence of acidity and saliency of crude oil on the viscosity reduction effect of the pour point depressants, so as to develop the pour point depressants capable of resisting acid and salt.
Disclosure of Invention
In order to solve the problems, the pour point depressant is prepared by polymerizing maleic acid, caffeic acid and indole monomers, and grafting and modifying ketone monomers and functional monomers, has simple synthesis process, can obtain higher pour point depressant and viscosity reducing effect, and has salt tolerance and acid tolerance of the pour point depressant.
According to one aspect of the present application, there is provided a pour point depressant having a structural formula as shown in formula (1):
wherein R is 1 、R 2 、R 3 、R 4 Each independently selectFrom any one of hydrogen, alkyl, alkoxy, hydroxy, ester, aryl, carboxyalkyl, hydroxyalkyl, alkoxyalkyl;
R 5 、R 6 each independently selected from any one of alkyl, carboxyalkyl, ester, hydroxyalkyl, nitrile, alkoxyalkyl, arylalkyl, alkanoyl, benzyloxymethyl;
R 7 、R 8 、R 9 each independently selected from any one of hydroxyl, formula (2) and formula (3):
x is selected from an integer between 5 and 10, y is selected from an integer between 20 and 30, z is selected from an integer between 10 and 15, and n is selected from an integer between 15 and 19.
Optionally, the R 1 、R 2 、R 3 、R 4 Each independently selected from any one of hydrogen, alkyl, alkoxy, hydroxyl and ester groups;
the R is 5 、R 6 Each independently selected from any one of carboxyalkyl, hydroxyalkyl and nitrile;
the x is 5, y is 30, and z is 12.
According to another aspect of the present application, there is provided a method for preparing the pour point depressant, comprising the steps of:
(1) The molar ratio is (20-30): (10-15): polymerizing fumaric acid, caffeic acid and indole monomers in the formula (5-10) to obtain an intermediate A;
(2) Reacting the intermediate A in the step (1) with a ketone monomer to obtain an intermediate B;
(3) Esterifying and/or amidating the intermediate B with a functional monomer to obtain the pour point depressant;
the structural formula of the indole monomer is shown as formula (4):
the structural formula of the ketone monomer is shown as formula (5):
the functional monomer is N, O-dimethylhydroxylamine hydrochloride or alcohol containing 16-20 carbon atoms.
Optionally, in the step (1), fumaric acid, caffeic acid, indole monomers and an initiator are dissolved in a solvent, uniformly stirred, protective gas is introduced, the temperature is raised to 60-65 ℃, the reaction is carried out for at least 5 hours, and a chain transfer agent is added to obtain the intermediate A.
Optionally, the initiator is any one or more of azo, persulfuric or peroxy initiators;
the solvent is any one or more of deionized water, ethanol, glycol, propanol, N-dimethylformamide, dimethyl sulfoxide, diethyl ether, formaldehyde and acetone;
the chain transfer agent is sodium formate.
Optionally, the ketone monomer is selected from any one or more of undecanone, 3, 4-hexanedione, levulinic acid, ethyl acetobutyrate, 4-hydroxy-2-butanone, 3-oxopentanone nitrile, pyruvonitrile, pivaloylacetonitrile, 5- (benzyloxy) -3-oxopentanone nitrile.
Optionally, the indole monomer is selected from any one or more of indole, 4-methylindole, 5-methylindole, 6-methylindole, 4-methoxyindole, 5-methoxyindole, 6-methoxyindole, 4-oxindole, 5-oxindole, 6-oxindole, 5-indolecarboxylic acid methyl ester, 5-indolecarboxylic acid and 6-indolecarboxylic acid.
Optionally, introducing a protective gas into the intermediate A in the step (1), adding a ketone monomer, a hydrogen source and a palladium catalyst, and reacting at 80-100 ℃ for 12-30h to obtain the intermediate B, wherein the molar ratio of the ketone monomer to the indole monomer is (3-5): 1.
optionally, the palladium-based catalyst is selected from palladium hydroxide/carbon or palladium hydroxide;
the hydrogen source is selected from any one or more of potassium formate, sodium formate and lithium formate.
Optionally, in the step (3), the intermediate B and N, O-dimethylhydroxylamine hydrochloride are subjected to amidation reaction for 16-24 hours at 30-40 ℃ under the action of a condensing agent to obtain the pour point depressant, wherein the molar ratio of the N, O-dimethylhydroxylamine hydrochloride to the caffeic acid is (4-8): 1, a step of; or (b)
The intermediate B and alcohol containing 16-20 carbon atoms are subjected to esterification reaction for 3-4 hours at 80-90 ℃ under the action of an esterification catalyst to obtain the pour point depressant, wherein the mole ratio of the alcohol containing 16-20 carbon atoms to the caffeic acid is (4-6): 1, a step of; or (b)
Carrying out esterification reaction on the intermediate B and alcohol containing 16-20 carbon atoms under the action of an esterification catalyst at 80-90 ℃ for 1-2h to obtain an intermediate C, wherein the molar ratio of the alcohol containing 16-20 carbon atoms to the caffeic acid is (2-3): 1, carrying out amidation reaction on the intermediate C and N, O-dimethylhydroxylamine hydrochloride for 12-16h at 30-40 ℃ under the action of a condensing agent to obtain the pour point depressant, wherein the molar ratio of the N, O-dimethylhydroxylamine hydrochloride to the caffeic acid is (2-4): 1.
optionally, the condensing agent is selected from any one or more of 1-hydroxybenzotriazole, 2- (7-azabenzotriazole) -N, N, N ', N' -tetramethylurea hexafluorophosphate, 1-hydroxy-7-azobenzotriazole, N, N-diisopropylethylamine, N-hydroxysuccinimide, tripyrrolidinyl phosphonium bromide hexafluorophosphate;
the alcohol containing 16-20 carbon atoms is a mixture of stearyl alcohol and eicosanol, and the molar ratio of the stearyl alcohol to the eicosanol is 1: (1-3).
Optionally, the esterification catalyst is any one or more of phosphoric acid, boric acid, sulfonic acid, toluenesulfonic acid, hydrochloric acid, hydrochloride, sulfuric acid and sulfate.
According to a further aspect of the present application there is provided the use of a pour point depressant according to any one of the above or a pour point depressant obtained by any one of the methods of manufacture, in the pour point depressant of waxy crude oils.
Benefits of the present application include, but are not limited to:
1. the pour point depressant of the application is prepared by polymerizing maleic acid, caffeic acid and indole monomers to obtain a polymer long chain, so that the molecular weight of the pour point depressant is moderate, the pour point depressant is uniformly dispersed in crude oil, the pour point depressant has pour point depressant and viscosity reducing effects on the crude oil, the chain links of a molecular chain are longer, the binding force with side chain groups is strong, the acid resistance and the salt resistance of the pour point depressant can be improved, and the application range of the pour point depressant is enlarged.
2. According to the pour point depressant prepared by the method, indole is used as one of the raw materials, benzene rings can be introduced into the pour point depressant, the rigidity of polymer molecular chains is increased, other groups are promoted to be tightly combined with wax crystals in crude oil, so that the pour point depressant can be wrapped on the surfaces of the wax crystals, and the growth of the wax crystals and the combination with other wax crystals are inhibited.
3. According to the pour point depressant prepared by the method, the prepolymer is grafted and modified by adopting the ketone and the functional monomer, so that the number of functional groups on a molecular chain of the pour point depressant can be increased, the adsorption effect on wax crystals is increased, and the pour point depressant and the viscosity reduction effect are improved.
4. According to the pour point depressant prepared by the method, the structure of wax crystals can be adjusted through the functional groups added by the ketone monomers, the branching degree of the pour point depressant is improved, and the action range of the pour point depressant is prolonged, so that the pour point depressant with less dosage can achieve higher pour point depressant and viscosity reduction effects.
5. According to the pour point depressant prepared by the application, the long polymer chain is a nonpolar group, so that the polymer chain can be uniformly dispersed in crude oil, the co-crystallization effect with wax crystals is improved, the polar groups on the side chains are uniformly dispersed in the pour point depressant, the growth of the wax crystals is fundamentally inhibited, the wax crystals are dispersed, and the fluidity of the crude oil is improved.
6. According to the pour point depressant prepared by the method, the intermediate B and the functional monomer are adopted for esterification and/or amidation, the carboxyl on fumaric acid and caffeic acid can be subjected to graft modification, and ester groups can be generated through esterification, so that the binding force with crude oil is increased, the dispersion of the pour point depressant in the crude oil is further promoted, amide groups can be introduced into a polymer side chain through amidation, the adsorptivity and dispersibility of wax crystals are improved, and when the pour point depressant contains both ester groups and amide groups, the pour point depressant effect on the crude oil is optimal.
7. According to the pour point depressant prepared by the application, carboxyl groups in fumaric acid and caffeic acid are not completely grafted and modified by the functional monomer, and the unmodified carboxyl groups can increase the hydrogen bonding effect of the pour point depressant, so that radial diffusion of wax crystals is inhibited, precipitation and growth of the wax crystals are prevented, but excessive carboxyl groups can cause poor viscosity reduction effect of crude oil, and therefore, the content of the carboxyl groups in the pour point depressant needs to be controlled by the functional monomer.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
The analytical method in the examples of the present application is as follows:
and (3) carrying out infrared spectrum analysis on the pour point depressant by using a Fourier transform infrared spectrometer, and carrying out test analysis on the pour point depressant by adopting an attenuated total reflection mode at room temperature.
Example 1
(1) 2.0mol of fumaric acid, 1.0mol of caffeic acid, 0.5mol of 4-methylindole and 0.05mol of azodiisobutyronitrile are respectively weighed and dissolved in a mixed solvent of 3L of deionized water and absolute ethyl alcohol, the volume ratio of the deionized water to the absolute ethyl alcohol is 1:1, nitrogen is introduced, the temperature is then raised to 65 ℃, and 0.5g of sodium formate is added after the reaction is carried out for 5 hours, so as to obtain an intermediate A;
(2) Continuously introducing nitrogen into the intermediate A in the step (1), adding 1.5mol of undecanone, 1.0mol of sodium formate and 0.1mol of palladium hydroxide/carbon, reacting for 12 hours at 100 ℃, and removing unreacted undecanone to obtain an intermediate B;
(3) 4.0mol of N, O-dimethylhydroxylamine hydrochloride, 3.0mol of 1-hydroxybenzotriazole, 3.0mol of 2- (7-azabenzotriazole) -N, N, N ', N' -tetramethylurea hexafluorophosphate, 1.5L of N, N-diisopropylethylamine and 1L of N, N-dimethylformamide are added into the intermediate B in the step (2), amidation reaction is carried out at 40 ℃ for 16 hours, and unreacted N, O-dimethylhydroxylamine hydrochloride is removed, so that the pour point depressant 1# is obtained.
Example 2
(1) 2.5mol of fumaric acid, 1.5mol of caffeic acid, 0.8mol of indole and 0.05mol of azodiisobutyronitrile are respectively weighed and dissolved in a mixed solvent of 3L of deionized water and absolute ethyl alcohol, the volume ratio of the deionized water to the absolute ethyl alcohol is 1:1, nitrogen is introduced, the temperature is then increased to 65 ℃, and 0.5g of sodium formate is added after 7 hours of reaction, so that an intermediate A is obtained;
(2) Continuously introducing nitrogen into the intermediate A in the step (1), adding 3.2mol of 3-oxopentanone nitrile, 2.0mol of sodium formate and 0.15mol of palladium hydroxide/carbon, reacting for 24 hours at 90 ℃, and removing unreacted 3-oxopentanone nitrile to obtain an intermediate B;
(3) Adding 1.0mol of stearyl alcohol, 3.0mol of eicosyl alcohol and 8.0g of phosphoric acid into the intermediate B in the step (2), carrying out esterification reaction for 1.5h at 80 ℃, removing unreacted stearyl alcohol and eicosyl alcohol to obtain an intermediate C, adding 5.0mol of N, O-dimethylhydroxylamine hydrochloride, 3.0mol of 1-hydroxybenzotriazole, 3.0mol of 2- (7-azabenzotriazole) -N, N, N ', N' -tetramethyl urea hexafluorophosphate, 1.5L of N, N-diisopropylethylamine and 1L of N, N-dimethylformamide into the intermediate C, carrying out amidation reaction for 14h at 40 ℃, and removing unreacted N, O-dimethylhydroxylamine hydrochloride to obtain a pour point depressant 2#.
Example 3
(1) Respectively weighing 3.0mol of fumaric acid, 1.0mol of caffeic acid, 1.0mol of 4-methoxyindole and 0.07mol of azodiisobutyronitrile, dissolving in a mixed solvent of 3L of deionized water and absolute ethyl alcohol, introducing nitrogen into the mixed solvent, heating to 60 ℃, reacting for 8 hours, and adding 0.5g of sodium formate to obtain an intermediate A;
(2) Continuously introducing nitrogen into the intermediate A in the step (1), adding 5.0mol of 4-hydroxy-2-butanone, 3.0mol of sodium formate and 0.2mol of palladium hydroxide/carbon, reacting for 30 hours at 80 ℃, and removing unreacted 4-hydroxy-2-butanone to obtain an intermediate B;
(3) Adding 2.0mol of stearyl alcohol, 3.0mol of eicosanol and 8.0g of phosphoric acid into the intermediate B in the step (2), carrying out esterification reaction for 3 hours at 90 ℃, and removing unreacted stearyl alcohol and eicosanol to obtain the pour point depressant 3#.
Example 4
The difference between this example and example 2 is that cyclohexanone is used instead of 3-oxopentanone nitrile in step (2), and the rest of the materials and steps are the same as in example 2, thus obtaining pour point depressant 4#.
Example 5
The difference between this example and example 2 is that levulinic acid is used instead of 3-oxopentanone nitrile in step (2), and the rest of the materials and steps are the same as in example 2, thus obtaining pour point depressant # 5.
Example 6
The difference between this example and example 2 is that in step (2), N-diisopropylethylamine is used instead of palladium hydroxide/carbon, and the rest of the materials are the same as in example 2, thus obtaining pour point depressant 6#.
Example 7
This example differs from example 2 in that in step (3), 4.0mol of stearyl alcohol, 2.0mol of arachidyl alcohol and 10.0g of phosphoric acid are added into intermediate B of step (2), esterification reaction is carried out for 4 hours at 80 ℃, and unreacted stearyl alcohol and arachidyl alcohol are removed, thus obtaining pour point depressant # 7.
Example 8
The difference between this example and example 1 is that in step (3), N, O-dimethylhydroxylamine hydrochloride was added in an amount of 6.0mol, and the remaining matters were the same as in example 1, to obtain pour point depressant 8#.
Example 9
This example differs from example 3 in that in step (3), the amount of stearyl alcohol added was 1.0mol, the amount of arachidyl alcohol was 1.5mol, and the remainder was the same as in example 3, to obtain pour point depressant 9#.
Comparative example 1
The comparative example was different from example 2 in that step (2) was not performed, and the substances in step (3) were added to intermediate a, and the substances and steps in step (1) and step (3) were the same as those in example 2, to obtain comparative pour point depressant d1#.
Comparative example 2
The difference between this comparative example and example 2 is that step (3) is not performed, i.e., intermediate B is the comparative pour point depressant d2#.
Comparative example 3
The difference between this comparative example and example 2 is that N-vinyl pyrrolidone was used instead of caffeic acid, and the rest of the materials and steps were the same as in example 2 to obtain a comparative pour point depressant D3#.
Test case
The pour point depressants prepared in examples and comparative examples were dissolved in crude oil for viscosity and congealing point measurement, the congealing point of crude oil samples was 35 ℃, the wax content was 25-26%, the gum and asphaltene content was 10-15%, and the viscosity was 1000-1500mpa·s. The specific operation is as follows: 0.1wt% pour point depressant was added to 99.9wt% crude oil at 60℃and stirred for 20 minutes, then cooled to room temperature and sampled for testing. The pour point of each crude oil added with pour point depressant is detected according to the GB/T510-1983 standard, and the viscosity is tested on crude oil containing pour point depressant at 60 ℃. The test results are shown in Table 1.
TABLE 1
| Sample of | Condensation point (DEG C) | Reducing amplitude (DEG C) | Viscosity (mPa. S) |
| Pour point depressingAgent 1# | 20 | 15 | 114 |
| Pour point depressant 2# | 16 | 19 | 84 |
| Pour point depressant 3# | 21 | 14 | 127 |
| Pour point depressant 4# | 23 | 12 | 151 |
| Pour point depressant 5# | 19 | 16 | 93 |
| Pour point depressant 6# | 25 | 10 | 182 |
| Pour point depressant 7# | 19 | 16 | 98 |
| Pour point depressant 8# | 24 | 11 | 170 |
| Pour point depressant 9# | 25 | 10 | 194 |
| Contrast pour point depressant D1# | 27 | 8 | 277 |
| Contrast pour point depressant D2# | 28 | 7 | 312 |
| Contrast pour point depressant D3# | 24 | 11 | 176 |
As can be seen from the data in Table 1, the pour point depressant of the present application can significantly reduce the congealing point and viscosity of crude oil when added to crude oil, wherein the pour point depressing effect of the graft modification treatment of intermediate B is optimal, and the pour point depressing range can be up to 19 ℃ by using N, O-dimethylhydroxylamine hydrochloride and an alcohol containing 16-20 carbon atoms in combination in example 2.
As can be seen from comparison of examples 4, 5 and example 2, the graft modification effect of ketone monomer on pour point depressant is greatly different, and the group containing carboxyl, hydroxyl, nitrile group and the like can obviously improve the pour point depressant effect, R 5 And R is 6 In the case of alkyl or cycloalkyl, the pour point depressing effect is reduced; as can be seen from a comparison of example 6 and example 2, in the graft modification of the pour point depressant with the ketone monomer, the catalyst is capable ofDetermining the final modification result, the catalyst of example 6 had poor catalytic activity on the reaction of the ketone monomer with the intermediate a, and therefore the number of modifying groups in pour point depressant 6# was reduced, and therefore the pour point depressing effect was reduced; as is clear from a comparison between example 7 and example 2, the graft modification of intermediate B can be achieved by the esterification reaction using only alcohol, but the combination modification of O-dimethylhydroxylamine hydrochloride and an alcohol having 16 to 20 carbon atoms results in a decrease in the graft modification rate, an increase in the carboxyl groups in the pour point depressant, and an increase in the number of long chain branches in the pour point depressant, and a decrease in the bonding force with wax crystals, which leads to a deterioration in the pour point depressant effect.
According to the test results of examples 8 and 9, it is found that the number of functional monomers is decreased, the amount of modified carboxyl groups in the pour point depressant is decreased, so that the number of carboxyl groups in the pour point depressant is increased, the hydrogen bonding action of the pour point depressant is enhanced, the pour point depressant and viscosity reducing effect are deteriorated, the number of modified carboxyl groups in the pour point depressant is increased, the number of carboxyl groups carried in the pour point depressant is decreased, and the radial diffusion of wax crystals cannot be inhibited, so that the pour point depressant and viscosity reducing effect are also deteriorated.
From the comparison of comparative example 1, comparative example 2 and example 2, it is known that the graft modification of the pour point depressant can increase the branching rate of the pour point depressant and the number of functional groups contained, thereby increasing the pour point depressing and viscosity reducing effects on crude oil; from the results of comparative example 3 and example 2, it is understood that the monomer on the main chain of the pour point depressant affects the pour point depressing effect of the pour point depressant, and N-vinylpyrrolidone does not participate in graft modification of the main chain in the latter stage, resulting in a decrease in the number of functional groups of the comparative pour point depressant D3# and thus a deterioration in the pour point depressing effect.
The foregoing is merely exemplary of the present application, and the scope of the present application is not limited to the specific embodiments, but is defined by the claims of the present application. Various modifications and changes may be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical ideas and principles of the present application should be included in the protection scope of the present application.
Claims (10)
1. The pour point depressant is characterized by being prepared by the following steps:
(1) 2.0mol of fumaric acid, 1.0mol of caffeic acid, 0.5mol of 4-methylindole and 0.05mol of azodiisobutyronitrile are respectively weighed and dissolved in a mixed solvent of 3L of deionized water and absolute ethyl alcohol, the volume ratio of the deionized water to the absolute ethyl alcohol is 1:1, nitrogen is introduced, the temperature is then raised to 65 ℃, and 0.5g of sodium formate is added after the reaction is carried out for 5 hours, so as to obtain an intermediate A;
(2) Continuously introducing nitrogen into the intermediate A in the step (1), adding 1.5mol of undecanone, 1.0mol of sodium formate and 0.1mol of palladium hydroxide/carbon, reacting for 12 hours at 100 ℃, and removing unreacted undecanone to obtain an intermediate B;
(3) 4.0mol of N, O-dimethylhydroxylamine hydrochloride, 3.0mol of 1-hydroxybenzotriazole, 3.0mol of 2- (7-azabenzotriazole) -N, N, N ', N' -tetramethylurea hexafluorophosphate, 1.5L of N, N-diisopropylethylamine and 1L of N, N-dimethylformamide are added into the intermediate B in the step (2), amidation reaction is carried out at 40 ℃ for 16h, and unreacted N, O-dimethylhydroxylamine hydrochloride is removed, thus obtaining the product.
2. The pour point depressant is characterized by being prepared by the following steps:
(1) 2.5mol of fumaric acid, 1.5mol of caffeic acid, 0.8mol of indole and 0.05mol of azodiisobutyronitrile are respectively weighed and dissolved in a mixed solvent of 3L of deionized water and absolute ethyl alcohol, the volume ratio of the deionized water to the absolute ethyl alcohol is 1:1, nitrogen is introduced, the temperature is then increased to 65 ℃, and 0.5g of sodium formate is added after 7 hours of reaction, so that an intermediate A is obtained;
(2) Continuously introducing nitrogen into the intermediate A in the step (1), adding 3.2mol of 3-oxopentanone nitrile, 2.0mol of sodium formate and 0.15mol of palladium hydroxide/carbon, reacting for 24 hours at 90 ℃, and removing unreacted 3-oxopentanone nitrile to obtain an intermediate B;
(3) Adding 1.0mol of stearyl alcohol, 3.0mol of eicosanol and 8.0g of phosphoric acid into the intermediate B in the step (2), carrying out esterification reaction for 1.5h at 80 ℃, removing unreacted stearyl alcohol and eicosanol to obtain an intermediate C, adding 5.0mol of N, O-dimethylhydroxylamine hydrochloride, 3.0mol of 1-hydroxybenzotriazole, 3.0mol of 2- (7-azabenzotriazole) -N, N, N ', N' -tetramethyl urea hexafluorophosphate, 1.5L of N, N-diisopropylethylamine and 1L of N, N-dimethylformamide into the intermediate C, carrying out amidation reaction for 14h at 40 ℃, and removing unreacted N, O-dimethylhydroxylamine hydrochloride to obtain the product.
3. The pour point depressant is characterized by being prepared by the following steps:
(1) Respectively weighing 3.0mol of fumaric acid, 1.0mol of caffeic acid, 1.0mol of 4-methoxyindole and 0.07mol of azodiisobutyronitrile, dissolving in a mixed solvent of 3L of deionized water and absolute ethyl alcohol, introducing nitrogen into the mixed solvent, heating to 60 ℃, reacting for 8 hours, and adding 0.5g of sodium formate to obtain an intermediate A;
(2) Continuously introducing nitrogen into the intermediate A in the step (1), adding 5.0mol of 4-hydroxy-2-butanone, 3.0mol of sodium formate and 0.2mol of palladium hydroxide/carbon, reacting for 30 hours at 80 ℃, and removing unreacted 4-hydroxy-2-butanone to obtain an intermediate B;
(3) Adding 2.0mol of stearyl alcohol, 3.0mol of eicosanol and 8.0g of phosphoric acid into the intermediate B in the step (2), carrying out esterification reaction for 3 hours at 90 ℃, and removing unreacted stearyl alcohol and eicosanol to obtain the product.
4. The pour point depressant is characterized by being prepared by the following steps:
(1) 2.5mol of fumaric acid, 1.5mol of caffeic acid, 0.8mol of indole and 0.05mol of azodiisobutyronitrile are respectively weighed and dissolved in a mixed solvent of 3L of deionized water and absolute ethyl alcohol, the volume ratio of the deionized water to the absolute ethyl alcohol is 1:1, nitrogen is introduced, the temperature is then increased to 65 ℃, and 0.5g of sodium formate is added after 7 hours of reaction, so that an intermediate A is obtained;
(2) Continuously introducing nitrogen into the intermediate A in the step (1), adding 3.2mol of cyclohexanone, 2.0mol of sodium formate and 0.15mol of palladium hydroxide/carbon, reacting at 90 ℃ for 24 hours, and removing unreacted cyclohexanone to obtain an intermediate B;
(3) Adding 1.0mol of stearyl alcohol, 3.0mol of eicosanol and 8.0g of phosphoric acid into the intermediate B in the step (2), carrying out esterification reaction for 1.5h at 80 ℃, removing unreacted stearyl alcohol and eicosanol to obtain an intermediate C, adding 5.0mol of N, O-dimethylhydroxylamine hydrochloride, 3.0mol of 1-hydroxybenzotriazole, 3.0mol of 2- (7-azabenzotriazole) -N, N, N ', N' -tetramethyl urea hexafluorophosphate, 1.5L of N, N-diisopropylethylamine and 1L of N, N-dimethylformamide into the intermediate C, carrying out amidation reaction for 14h at 40 ℃, and removing unreacted N, O-dimethylhydroxylamine hydrochloride to obtain the product.
5. The pour point depressant is characterized by being prepared by the following steps:
(1) 2.5mol of fumaric acid, 1.5mol of caffeic acid, 0.8mol of indole and 0.05mol of azodiisobutyronitrile are respectively weighed and dissolved in a mixed solvent of 3L of deionized water and absolute ethyl alcohol, the volume ratio of the deionized water to the absolute ethyl alcohol is 1:1, nitrogen is introduced, the temperature is then increased to 65 ℃, and 0.5g of sodium formate is added after 7 hours of reaction, so that an intermediate A is obtained;
(2) Continuously introducing nitrogen into the intermediate A in the step (1), adding 3.2mol of levulinic acid, 2.0mol of sodium formate and 0.15mol of palladium hydroxide/carbon, reacting for 24 hours at 90 ℃, and removing unreacted levulinic acid to obtain an intermediate B;
(3) Adding 1.0mol of stearyl alcohol, 3.0mol of eicosanol and 8.0g of phosphoric acid into the intermediate B in the step (2), carrying out esterification reaction for 1.5h at 80 ℃, removing unreacted stearyl alcohol and eicosanol to obtain an intermediate C, adding 5.0mol of N, O-dimethylhydroxylamine hydrochloride, 3.0mol of 1-hydroxybenzotriazole, 3.0mol of 2- (7-azabenzotriazole) -N, N, N ', N' -tetramethyl urea hexafluorophosphate, 1.5L of N, N-diisopropylethylamine and 1L of N, N-dimethylformamide into the intermediate C, carrying out amidation reaction for 14h at 40 ℃, and removing unreacted N, O-dimethylhydroxylamine hydrochloride to obtain the product.
6. The pour point depressant is characterized by being prepared by the following steps:
(1) 2.5mol of fumaric acid, 1.5mol of caffeic acid, 0.8mol of indole and 0.05mol of azodiisobutyronitrile are respectively weighed and dissolved in a mixed solvent of 3L of deionized water and absolute ethyl alcohol, the volume ratio of the deionized water to the absolute ethyl alcohol is 1:1, nitrogen is introduced, the temperature is then increased to 65 ℃, and 0.5g of sodium formate is added after 7 hours of reaction, so that an intermediate A is obtained;
(2) Continuously introducing nitrogen into the intermediate A in the step (1), adding 3.2mol of 3-oxopentanone nitrile, 2.0mol of sodium formate and 0.15mol of N, N-diisopropylethylamine, reacting for 24 hours at 90 ℃, and removing unreacted 3-oxopentanone nitrile to obtain an intermediate B;
(3) Adding 1.0mol of stearyl alcohol, 3.0mol of eicosanol and 8.0g of phosphoric acid into the intermediate B in the step (2), carrying out esterification reaction for 1.5h at 80 ℃, removing unreacted stearyl alcohol and eicosanol to obtain an intermediate C, adding 5.0mol of N, O-dimethylhydroxylamine hydrochloride, 3.0mol of 1-hydroxybenzotriazole, 3.0mol of 2- (7-azabenzotriazole) -N, N, N ', N' -tetramethyl urea hexafluorophosphate, 1.5L of N, N-diisopropylethylamine and 1L of N, N-dimethylformamide into the intermediate C, carrying out amidation reaction for 14h at 40 ℃, and removing unreacted N, O-dimethylhydroxylamine hydrochloride to obtain the product.
7. The pour point depressant is characterized by being prepared by the following steps:
(1) 2.5mol of fumaric acid, 1.5mol of caffeic acid, 0.8mol of indole and 0.05mol of azodiisobutyronitrile are respectively weighed and dissolved in a mixed solvent of 3L of deionized water and absolute ethyl alcohol, the volume ratio of the deionized water to the absolute ethyl alcohol is 1:1, nitrogen is introduced, the temperature is then increased to 65 ℃, and 0.5g of sodium formate is added after 7 hours of reaction, so that an intermediate A is obtained;
(2) Continuously introducing nitrogen into the intermediate A in the step (1), adding 3.2mol of 3-oxopentanone nitrile, 2.0mol of sodium formate and 0.15mol of palladium hydroxide/carbon, reacting for 24 hours at 90 ℃, and removing unreacted 3-oxopentanone nitrile to obtain an intermediate B;
(3) Adding 4.0mol of stearyl alcohol, 2.0mol of eicosanol and 10.0g of phosphoric acid into the intermediate B in the step (2), carrying out esterification reaction for 4 hours at 80 ℃, and removing unreacted stearyl alcohol and eicosanol to obtain the product.
8. The pour point depressant is characterized by being prepared by the following steps:
(1) 2.0mol of fumaric acid, 1.0mol of caffeic acid, 0.5mol of 4-methylindole and 0.05mol of azodiisobutyronitrile are respectively weighed and dissolved in a mixed solvent of 3L of deionized water and absolute ethyl alcohol, the volume ratio of the deionized water to the absolute ethyl alcohol is 1:1, nitrogen is introduced, the temperature is then raised to 65 ℃, and 0.5g of sodium formate is added after the reaction is carried out for 5 hours, so as to obtain an intermediate A;
(2) Continuously introducing nitrogen into the intermediate A in the step (1), adding 1.5mol of undecanone, 1.0mol of sodium formate and 0.1mol of palladium hydroxide/carbon, reacting for 12 hours at 100 ℃, and removing unreacted undecanone to obtain an intermediate B;
(3) To intermediate B of step (2), 6.0mol of N, O-dimethylhydroxylamine hydrochloride, 3.0mol of 1-hydroxybenzotriazole, 3.0mol of 2- (7-azabenzotriazole) -N, N, N ', N' -tetramethylurea hexafluorophosphate, 1.5L of N, N-diisopropylethylamine and 1L of N, N-dimethylformamide were added, amidation reaction was performed at 40℃for 16 hours, and unreacted N, O-dimethylhydroxylamine hydrochloride was removed to obtain the final product.
9. The pour point depressant is characterized by being prepared by the following steps:
(1) Respectively weighing 3.0mol of fumaric acid, 1.0mol of caffeic acid, 1.0mol of 4-methoxyindole and 0.07mol of azodiisobutyronitrile, dissolving in a mixed solvent of 3L of deionized water and absolute ethyl alcohol, introducing nitrogen into the mixed solvent, heating to 60 ℃, reacting for 8 hours, and adding 0.5g of sodium formate to obtain an intermediate A;
(2) Continuously introducing nitrogen into the intermediate A in the step (1), adding 5.0mol of 4-hydroxy-2-butanone, 3.0mol of sodium formate and 0.2mol of palladium hydroxide/carbon, reacting for 30 hours at 80 ℃, and removing unreacted 4-hydroxy-2-butanone to obtain an intermediate B;
(3) Adding 1.0mol of stearyl alcohol, 1.5mol of eicosanol and 8.0g of phosphoric acid into the intermediate B in the step (2), carrying out esterification reaction for 3 hours at 90 ℃, and removing unreacted stearyl alcohol and eicosanol to obtain the product.
10. Use of a pour point depressant according to any one of claims 1 to 9 for pour point depression of waxy crude oil.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0400868A1 (en) * | 1989-05-30 | 1990-12-05 | Exxon Chemical Patents Inc. | Multifunctional viscosity index improver exhibiting improved low temperature viscometric properties |
| CN113480989A (en) * | 2021-06-02 | 2021-10-08 | 德仕能源科技集团股份有限公司 | Quadripolymer pour point depressant for high-freezing-point crude oil and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0400868A1 (en) * | 1989-05-30 | 1990-12-05 | Exxon Chemical Patents Inc. | Multifunctional viscosity index improver exhibiting improved low temperature viscometric properties |
| CN113480989A (en) * | 2021-06-02 | 2021-10-08 | 德仕能源科技集团股份有限公司 | Quadripolymer pour point depressant for high-freezing-point crude oil and preparation method thereof |
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