CN108192004B - Quadripolymer, preparation method thereof and application thereof in crude oil pour point depressant - Google Patents
Quadripolymer, preparation method thereof and application thereof in crude oil pour point depressant Download PDFInfo
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Abstract
A tetrapolymer for use in the pour point depression of crude oil comprising structural units derived from: maleic acid derivatives, polar vinyl compounds, high carbon alpha-olefins and ethylene. The molar ratio of the maleic acid derivative to the polar vinyl compound to the high-carbon alpha-olefin to ethylene is 1: 1-5: 1-2: 10-30, the maleic acid derivative is obtained by reacting maleic anhydride with an amine compound, and the amine compound is C8-50 monohydric aliphatic amine, C8-50 dihydric aliphatic amine or C8-50 fatty alcohol amine. The polar vinyl compound is at least one selected from acrylic acid, acrylamide, styrene sulfonic acid, sodium styrene sulfonate, propylene sulfonic acid and sodium propylene sulfonate. The high-carbon alpha-olefin is an alpha-olefin having 8 to 50 carbon atoms. The crude oil pour point depressant containing the quadripolymer has good pour point depressing and viscosity reducing effects on high-wax crude oil and high-viscosity crude oil.
Description
Technical Field
The invention relates to the field of oil additives, in particular to a quadripolymer, a preparation method thereof and application thereof in a pour point depressant for crude oil.
Background
Petroleum (crude oil) is a main energy source used by human beings, is also an important chemical raw material, and plays a very important role in national economy. Most of oil fields in China are in the middle and later stages of development, the content of heavy components in produced crude oil is higher and higher, and the problems of easy wax deposition, high condensation point, high viscosity, poor fluidity, large pipe transportation resistance and the like are caused in the processes of mining, gathering and transportation and the like.
The addition of the chemical pour point depressant can effectively prevent paraffin from crystallizing, improve the flowability of the crude oil, effectively avoid the problems of high energy consumption of pipeline heating, difficult restart after the stop of transportation in a heating method and the like, and is an effective way for realizing normal-temperature transportation of the waxy crude oil, reducing the energy consumption of pipeline transportation and solving the problems of exploitation and transportation of the highly waxy crude oil. However, with continuous exploitation of crude oil in China, the phenomenon of crude oil heaviness and deterioration is increasingly serious, and the traditional pour point depressant has a plurality of problems in use, mainly including: 1) poor suitability, often one agent is effective on one crude oil and not on another; 2) in field use, the influence of the temperature rise of the crude oil on low-temperature rheological property is large, and a temperature rise deterioration area exists; 3) the treatment effect on high wax, colloid and asphaltene crude oil or thick oil is poor. Therefore, developing a pour point depressant suitable for the crude oil condition in China is an urgent and difficult task in the field of current oil additives.
Disclosure of Invention
In view of the above, there is a need to provide a tetrapolymer, a preparation method thereof and an application thereof in a pour point depressant for crude oil, aiming at the problem of poor flowability of crude oil.
A tetrapolymer for use in the pour point depression of crude oil comprising structural units derived from:
a maleic acid derivative;
a polar vinyl compound;
high carbon alpha-olefins; and
ethylene;
the molar ratio of the maleic acid derivative, the polar vinyl compound, the high-carbon alpha-olefin and the ethylene is 1: 1-5: 1-2: 10-30;
the maleic acid derivative is obtained by carrying out amidation reaction on maleic anhydride and an amine compound, wherein the amine compound is fatty amine or fatty alcohol amine, the fatty amine is monoamine with 8-50 carbon atoms or diamine with 8-50 carbon atoms, and the fatty alcohol amine is alcohol amine with 8-50 carbon atoms;
the polar vinyl compound is selected from at least one of acrylic acid, acrylamide, acrylic sulfonic acid, sodium propylene sulfonate, p-styrene sulfonic acid and sodium p-styrene sulfonate;
the high-carbon alpha-olefin is alpha-olefin with 8-50 carbon atoms.
The quadripolymer has a long alkyl main chain and a side chain, can play a role of a crystal nucleus, is easy to be eutectic with wax at low temperature to form a large number of microcrystals, and reduces the formation of large wax clusters; the quadripolymer also contains a large number of polar groups such as amide groups, amino groups, carboxyl groups or sulfonic groups, and the like, in the wax crystal growth stage, nonpolar long-chain alkyl groups are eutectic with colloid and asphaltene, the polar groups are distributed on the surface of the wax crystal, and the repulsion of charges prevents crystal particles from approaching each other, so that the growth direction, crystal structure and the like of the wax crystal in the growth process are changed, a wax crystal structure with small surface energy and low structural strength is easily formed, and the condensation point of crude oil is reduced. The polar group and the long alkyl chain have the combined action in the process of reducing the pour point and the viscosity of the crude oil, so that the pour point and the viscosity of the crude oil are effectively reduced; and the long alkyl chain has better space extension effect and shielding effect, and strong polar groups form adsorption micelles by self-aggregation to adsorb colloid and asphaltene, prevent wax crystal growth and increase the fluidity of the crude oil.
In one embodiment, the aliphatic amine is a monoamine with 18-36 carbon atoms or a diamine with 18-36 carbon atoms, and the aliphatic alcohol amine is alcohol amine with 18-36 carbon atoms; and/or
The high-carbon alpha-olefin is alpha-olefin with 18-36 carbon atoms; and/or
The number average molecular weight of the quadripolymer is 5000-100000.
The preparation method of the quadripolymer comprises the following steps: and (3) carrying out copolymerization reaction on the maleic acid derivative, the polar vinyl compound, the high-carbon alpha-olefin and the ethylene to obtain the quadripolymer.
The preparation method of the quadripolymer has the advantages of simple operation, easily obtained raw materials and low cost.
In one embodiment, the maleic acid derivative is prepared by the following steps: dissolving the maleic anhydride and the amine compound in a solvent, heating to 45-50 ℃, adding a catalyst, continuously heating to 90-130 ℃, and carrying out amidation reaction for 2-8 hours to obtain the maleic acid derivative.
In one embodiment, the step of copolymerizing the maleic acid derivative, the polar vinyl compound, the high-carbon α -olefin, and the ethylene to obtain the tetrapolymer specifically comprises: dissolving the maleic acid derivative, the polar vinyl compound, the high-carbon alpha-olefin and the ethylene in a solvent, heating to 45-50 ℃ under a protective atmosphere, adding an initiator, continuously heating to 75-100 ℃, reacting for 3-10 hours, and desolventizing to obtain the quadripolymer.
In one embodiment, the initiator is at least one selected from the group consisting of diisopropyl peroxydicarbonate, dibenzoyl peroxide, azobisisobutyronitrile, di-t-butyl peroxide, cumene hydroperoxide, and cyclohexanone peroxide, and the mass of the initiator is 0.1% to 1% of the total mass of the maleic acid derivative, the polar vinyl compound, the high-carbon α -olefin, and the ethylene.
The application of the quadripolymer in pour point depressing of crude oil.
The pour point depressant for crude oil comprises the following components in parts by weight:
the high-wax crude oil is a mixture of hydrocarbons with different carbon numbers, the distribution range is wide, and the quadripolymer can be matched with components with different carbon numbers in the crude oil by compounding, so that the application range of the pour point depressant is widened, and the comprehensive pour point depressing and viscosity reducing effects of the product are improved.
The wax crystal dispersing agent plays a role in dispersing wax crystals, so that the wax crystals are uniformly dispersed, and the adhesion among the wax crystals is weakened.
The colloid and asphaltene molecules are the components with the largest molecular weight and the strongest polarity in the crude oil, and because hydrogen bonds are formed among the molecules, the molecular planes are overlapped and stacked to generate strong cohesive force, so that the internal friction force when the crude oil molecules are subjected to relative displacement is large, the crude oil has high viscosity, the low-temperature fluidity of the high-viscosity crude oil is poor, and a plurality of adverse effects are generated on the exploitation and the transportation of the crude oil. The hydrogen bond inhibitor can form stronger hydrogen bonds with polar groups in the colloid and the asphaltene, destroy the tight planar stacking between the colloid and the asphaltene molecules, and form an aggregate which is randomly stacked, has a loose structure, has a reduced ordering degree and takes part in inhibitor molecules, thereby achieving the effects of pour point depression and viscosity reduction.
The drag reducer can effectively improve the drag reduction effect of crude oil, particularly thick oil, and reduce the flow resistance in crude oil exploitation or pipeline transportation.
The dispersion stabilizer has the main function of changing the surface properties of macromolecular colloid and asphaltene in the crude oil, so that the dispersion stabilizer can be uniformly dispersed in the crude oil, and the crude oil has good rheological property and stability.
The crude oil contains a small amount of water, and the addition of the emulsifier can change the surface tension between water and the crude oil, so that a uniform and stable dispersion system is formed, and the flow resistance is reduced.
In one embodiment, the maleic ester-vinyl acetate-styrene-ethylene copolymer has a number average molecular weight of 2000 to 10000.
In one embodiment, the wax crystal dispersant is a polycarboxylic acid derivative.
In one embodiment, the polycarboxylic acid derivative is selected from at least one of the following:
in one embodiment, the hydrogen bond inhibitor is a polyol.
In one embodiment, the hydrogen bond inhibitor is selected from at least one of ethylene glycol, propylene glycol, glycerol, butylene glycol, pentylene glycol, hexylene glycol, pentaerythritol, xylitol, and sorbitol.
In one embodiment, the drag reducer is poly alpha-olefin with 8-36 carbon atoms.
In one embodiment, the dispersion stabilizer is lignosulfonate or polynaphthalene sulfonate, and further, the dispersion stabilizer is sodium lignosulfonate or polynaphthalene sulfonate.
In one embodiment, the emulsifier is selected from at least one of sorbitan oleic acid, sorbitan palmitic acid, sodium dodecylbenzene sulfonate, glyceryl stearate, polyoxyethylene monostearate, polyoxyethylene lauryl ether, polyoxyethylene cetyl alcohol, and polyethylene glycol fatty acid ester.
Detailed Description
To facilitate an understanding of the present invention, the invention is described below in connection with tetrapolymers, methods of making the same, and use in crude oil pour point depressants. Some examples of the invention are given herein. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
The quadripolymer of the embodiment is used for reducing the pour point of crude oil and is a structural unit obtained by the following compounds: maleic acid derivatives, polar vinyl compounds, high carbon alpha-olefins and ethylene. The molar ratio of the maleic acid derivative, the polar vinyl compound, the high-carbon alpha-olefin and the ethylene is 1: 1-5: 1-2: 10-30.
In one embodiment, the molar ratio of the maleic acid derivative, the polar vinyl compound, the high-carbon alpha-olefin and the ethylene is 1:1 to 4:1 to 2:15 to 25.
Preferably, the molar ratio of the maleic acid derivative, the polar vinyl compound, the high-carbon alpha-olefin and the ethylene is 1:1 to 3:1:20 to 25.
The maleic acid derivative is obtained by amidation reaction of maleic anhydride and an amine compound, wherein the amine compound is fatty amine or fatty alcohol amine, the fatty amine is monoamine with 8-50 carbon atoms or diamine with 8-50 carbon atoms, and the fatty alcohol amine is alcohol amine with 8-50 carbon atoms.
In one embodiment, the aliphatic amine is a C18-36 monoamine or a C18-36 diamine, and the aliphatic alcohol amine is an alcohol amine with C18-36.
Preferably, the fatty amine or fatty alcohol amine is at least one selected from the group consisting of octadecylamine, tetracosane, dotriacontamine, 1, 18-octadecanediamine, 1, 24-tetracosane, and 24-amino-1-tetracosanol.
The polar vinyl compound is at least one selected from acrylic acid, acrylamide, acrylic sulfonic acid, sodium acrylic sulfonate, p-styrene sulfonic acid and sodium p-styrene sulfonate.
Preferably, the polar vinyl compound is acrylic acid, acrylamide or p-styrenesulfonic acid, and more preferably, the polar vinyl compound is acrylamide.
The high-carbon alpha-olefin is an alpha-olefin having 8 to 50 carbon atoms.
In one embodiment, the high-carbon alpha-olefin is an alpha-olefin with 18-36 carbon atoms.
Preferably, the higher alpha-olefin is selected from at least one of 1-eicosene, 1-eicosadiene, and 1-tetracosene.
In one embodiment, the number average molecular weight of the tetrapolymer is 5000 to 100000. Preferably, the number average molecular weight of the tetrapolymer is 20000 to 50000.
The quadripolymer has a long alkyl main chain and a side chain, can play a role of a crystal nucleus, is easy to be eutectic with wax at low temperature to form a large number of microcrystals, and reduces the formation of large wax clusters; the quadripolymer also contains a large number of polar groups such as amide groups, amino groups, carboxyl groups or sulfonic groups, and the like, in the wax crystal growth stage, nonpolar long-chain alkyl groups are eutectic with colloid and asphaltene, the polar groups are distributed on the surface of the wax crystal, and the repulsion of charges prevents crystal particles from approaching each other, so that the growth direction, crystal structure and the like of the wax crystal in the growth process are changed, a wax crystal structure with small surface energy and low structural strength is easily formed, and the condensation point of crude oil is reduced. The polar group and the long alkyl chain have the combined action in the process of reducing the pour point and the viscosity of the crude oil, so that the pour point and the viscosity of the crude oil are effectively reduced; and the long alkyl chain has better space extension effect and shielding effect, and strong polar groups form adsorption micelles by self-aggregation to adsorb colloid and asphaltene, prevent wax crystal growth and increase the fluidity of the crude oil.
The preparation method of the quadripolymer comprises the following steps:
s110, preparing the maleic acid derivative by using maleic anhydride and amine compounds.
In one embodiment, maleic anhydride and an amine compound are dissolved in a solvent, heated to 45-50 ℃, added with a catalyst, continuously heated to 90-130 ℃, subjected to amidation reaction for 2-8 hours to obtain a reaction initial product, and separated and purified to obtain the maleic acid derivative.
The amine compound is fatty amine or fatty alcohol amine, wherein the fatty amine is monoamine with 8-50 carbon atoms or diamine with 8-50 carbon atoms, and the fatty alcohol amine is alcohol amine with 8-50 carbon atoms. Preferably, the aliphatic amine is a monoamine with 18-36 carbon atoms or a diamine with 18-36 carbon atoms, and the aliphatic alcohol amine is alcohol amine with 18-36 carbon atoms. More preferably, the aliphatic amine is a monoamine having 24 to 32 carbon atoms or a diamine having 24 to 32 carbon atoms, and the aliphatic alcohol amine is an alcohol amine having 24 to 32 carbon atoms. Further preferably, the fatty amine is selected from the group consisting of tetracosane, dotriacontamine and 1, 24-tetracosane, and the fatty alcohol amine is selected from the group consisting of 24-amino-1-tetracosanol.
The molar ratio of the maleic anhydride to the amine compound is 1: 1-2.2, preferably 1:1 to 2.
In the present embodiment, the catalyst is p-toluenesulfonic acid, and the amount of the catalyst is 0.5% to 5% by mass of maleic anhydride. In other embodiments, the catalyst may also be concentrated sulfuric acid, sulfamic acid, or other acid catalysts commonly used in the art for esterification or amidation reactions.
The solvent is at least one of petroleum ether, toluene, xylene, mixed trimethylbenzene or heavy aromatic hydrocarbon. The mass of the solvent added is 0.5 to 3 times of the total mass of the maleic anhydride and the amine compound.
The specific steps of separation and purification comprise: washing the reaction initial product with water, drying, and desolventizing to obtain the maleic acid derivative.
S120, carrying out copolymerization reaction on the maleic acid derivative, the polar vinyl compound, the high-carbon alpha-olefin and the ethylene to obtain the quadripolymer.
In one embodiment, the maleic acid derivative, the polar vinyl compound, the high-carbon alpha-olefin and the ethylene are dissolved in a solvent, the temperature is raised to 45-50 ℃ under the protective atmosphere, an initiator is added, the temperature is continuously raised to 75-100 ℃, the reaction is carried out for 3-10 hours, and finally the solvent is removed to obtain the quadripolymer.
Specifically, the polar vinyl compound is at least one selected from acrylic acid, acrylamide, styrene sulfonic acid, sodium styrene sulfonate, propylene sulfonic acid and sodium propylene sulfonate. Preferably, the polar vinyl compound is acrylic acid, acrylamide or p-styrenesulfonic acid, and more preferably, the polar vinyl compound is acrylamide.
Specifically, the high-carbon alpha-olefin is an alpha-olefin having 8 to 50 carbon atoms. Preferably, the high-carbon alpha-olefin is an alpha-olefin having 18 to 36 carbon atoms. It is further preferred that the higher alpha-olefin is 1-eicosene, 1-eicosadiene or 1-tetracosene.
Specifically, the molar ratio of the maleic acid derivative, the polar vinyl compound, the high-carbon alpha-olefin and the ethylene is 1:1 to 5:1 to 2:10 to 30. Preferably, the molar ratio of the maleic acid derivative, the polar vinyl compound, the high-carbon alpha-olefin and the ethylene is 1:1 to 4:1 to 2:15 to 25. More preferably, the molar ratio of the maleic acid derivative, the polar vinyl compound, the high-carbon alpha-olefin and the ethylene is 1:1 to 3:1:20 to 25.
Specifically, the initiator is at least one selected from the group consisting of diisopropyl peroxydicarbonate, dibenzoyl peroxide, azobisisobutyronitrile, di-t-butyl peroxide, cumene hydroperoxide, and cyclohexanone peroxide. The added mass of the initiator is 0.1-1% of the total mass of the maleic acid derivative, the polar vinyl compound, the high-carbon alpha-olefin and the ethylene. Of course, in other embodiments, the initiator may also be azobisisoheptonitrile, cyclohexanone peroxide, or dimethyl azobisisobutyrate. It will be appreciated that the maleic acid derivative, polar vinyl compound, high carbon alpha-olefin and ethylene described above have been dissolved and mixed well before the initiator is added.
In this embodiment, the protective atmosphere is nitrogen, and in other embodiments, the protective atmosphere may be argon.
Specifically, the solvent is at least one of petroleum ether, toluene, xylene, mixed trimethylbenzene or heavy aromatic hydrocarbon, and the added mass of the solvent is 0.5 to 3 times of the total mass of the maleic acid derivative, the polar vinyl compound, the high-carbon alpha-olefin and the ethylene.
Specifically, the number average molecular weight of the tetrapolymer prepared by the preparation method of the tetrapolymer is 5000-100000. Preferably, the number average molecular weight of the tetrapolymer is 20000 to 50000.
The application of the quadripolymer in pour point depressing of crude oil.
The quadripolymer is used for crude oil, so that the condensation point and the viscosity of the crude oil can be reduced, and the low-temperature fluidity of the crude oil can be improved.
The pour point depressant for crude oil comprises the following components in parts by weight:
the crude oil is a mixture of hydrocarbons with different carbon numbers, the distribution range is wide, and the four-component copolymer can enhance the matching property with components with different carbon numbers in the crude oil by compounding. The maleic ester-vinyl acetate-styrene-ethylene copolymer mainly aims at the pour point depression of crude oil with low carbon number, the quadripolymer has good pour point depression effect on wax components with high carbon number in the crude oil, the application range of the pour point depressant is widened by compounding the maleic ester-vinyl acetate-styrene-ethylene copolymer and the quadripolymer, and the comprehensive pour point depression effect of products is improved.
In one embodiment, the crude oil pour point depressant comprises the following components in parts by weight:
specifically, the number average molecular weight of the maleic ester-vinyl acetate-styrene-ethylene copolymer is 2000-10000.
Specifically, the wax crystal dispersing agent is a polycarboxylic acid derivative and is selected from at least one of L1-L6:
the wax crystal dispersing agent has the function of dispersing wax crystals, so that the wax crystals are uniformly dispersed, and the adhesion among the wax crystals is weakened.
The colloid and asphaltene molecules are the components with the largest molecular weight and the strongest polarity in the crude oil, and because hydrogen bonds are formed among the molecules, the molecular planes are overlapped and stacked to generate strong cohesive force, so that the internal friction force when the crude oil molecules are subjected to relative displacement is large, the crude oil has high viscosity, the low-temperature fluidity of the high-viscosity crude oil is poor, and a plurality of adverse effects are generated on the exploitation and the transportation of the crude oil.
Specifically, the hydrogen bond inhibitor is at least one selected from the group consisting of ethylene glycol, propylene glycol, glycerol, butylene glycol, pentylene glycol, hexylene glycol, pentaerythritol, xylitol, and sorbitol. Preferably, the hydrogen bond inhibitor is ethylene glycol, propylene glycol, glycerol, butylene glycol, pentaerythritol, xylitol or sorbitol. Further preferably, the hydrogen bond inhibitor is pentaerythritol, xylitol or sorbitol.
The hydrogen bond inhibitor can form stronger hydrogen bonds with polar groups in the colloid and the asphaltene, destroy the tight planar stacking between the colloid and the asphaltene molecules, and form an aggregate which is randomly stacked, has a loose structure, has a reduced ordering degree and takes part in inhibitor molecules, thereby achieving the effects of pour point depression and viscosity reduction.
Specifically, the drag reducer is poly-alpha-olefin with 8-36 carbon atoms, and the number average molecular weight is 2000000-20000000. Preferably, the drag reducer is poly-alpha-olefin with 5000000-15000000 carbon atoms, and the number average molecular weight is 8000000-12000000. More preferably, the drag reducer is polydecene, polydodecene, polytetradecene or polyhexadecene, and the number average molecular weight is 8000000-10000000.
The drag reducer can effectively improve the drag reduction effect of crude oil, particularly thick oil, and reduce the flow resistance in crude oil exploitation or pipeline transportation.
Specifically, the dispersion stabilizer is selected from lignosulfonate polynaphthalenesulfonates. Preferably, the dispersion stabilizer is sodium lignosulfonate or sodium polynaphthalene sulfonate.
The dispersion stabilizer has the main function of changing the surface properties of macromolecular colloid and asphaltene so as to ensure that the macromolecular colloid and the asphaltene are uniformly dispersed in the crude oil and the crude oil has good rheology and stability.
Specifically, the emulsifier is at least one selected from sorbitan oleic acid, sorbitan palmitic acid, sodium dodecylbenzene sulfonate, glyceryl stearate, polyoxyethylene monostearate, polyoxyethylene lauryl ether, polyoxyethylene cetyl alcohol and polyethylene glycol fatty acid ester, and preferably, the emulsifier is sorbitan palmitic acid, sodium dodecylbenzene sulfonate or polyethylene glycol fatty acid ester.
The crude oil contains a small amount of water, and the addition of the emulsifier can change the surface tension between water and the crude oil, so that a uniform and stable dispersion system is formed, and the flow resistance is reduced.
Specifically, the diluent is at least one of gasoline, diesel oil, toluene, xylene, mixed trimethylbenzene and heavy aromatics. Further, the diluent is diesel oil, toluene, xylene, mixed trimethylbenzene or heavy aromatic hydrocarbon. The diluent is preferably diesel oil or mesitylene.
The crude oil pour point depressant has wide application range, stable performance and good compatibility with oil products and other additives, can obviously reduce the pour point and the viscosity of crude oil, is suitable for the crude oil with different wax contents, and also has good pour point depressing and viscosity reducing effects on high-colloid and asphaltene crude oil.
The crude oil pour point depressant is prepared by uniformly mixing the components.
The preparation method of the crude oil pour point depressant has simple process and little three-waste pollution.
When the crude oil pour point depressant is used, the crude oil pour point depressant is added into crude oil according to the dosage of 50ppm to 1000ppm and is uniformly mixed, the use method is simple and easy to implement, and the addition of the crude oil pour point depressant can obviously reduce the pour point and viscosity of the crude oil and improve the low-temperature fluidity of the crude oil.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
Dissolving 0.1mol of maleic anhydride and a1mol of amine compound A (A for short in the table) in dimethylbenzene (the mass of the amine compound A is equivalent to that of the reaction raw material), heating to 45 ℃, adding p-toluenesulfonic acid accounting for 1% of the mass of the maleic anhydride after the maleic anhydride and the amine compound A are dissolved and stirred uniformly, continuing heating to 100 ℃, and reacting for 5 hours; then washing to neutrality, drying and desolventizing to obtain the maleic acid derivative.
Dissolving the maleic acid derivative, acrylic acid, 1-eicosene and ethylene in dimethylbenzene (the mass of the reaction raw materials is equivalent) according to the molar ratio of 1:1:1:10, heating to 45 ℃ under the protection of nitrogen, adding azobisisobutyronitrile after the reactants are dissolved and stirred uniformly, continuing heating to 80 ℃, reacting for 7 hours, and distilling under reduced pressure to remove the solvent to obtain the quadripolymer.
Taking 20 parts of the tetrapolymer prepared above, 20 parts of maleate-vinyl acetate-styrene-ethylene copolymer (with the number average molecular weight of 4000) and 10 parts of wax crystal dispersing agent L1 (namely, wax crystal dispersing agent L1)
) 8 parts of ethylene glycol and 20 parts of diesel oil are uniformly mixed to prepare the crude oil pour point depressants from #1 to # 12.
Adding the prepared crude oil pour point depressants #1 to #12 into Daqing crude oil according to the dosage of 100ppm respectively; daqing crude oil has a congealing point of 32 deg.C and an apparent viscosity of 894mPa · s (25 deg.C); the crude oil treatment temperature is 60 ℃, the final cooling temperature is 20 ℃, the shearing rate is 1200r/min, shearing is 1min, heating is repeated for 2 times, the cooling rate is 0.3 ℃/min, and the final cooling temperature is kept stand for 24 h; the congealing point was measured by a congealing point measuring instrument in accordance with GB/T510-83, and the viscosity of the crude oil was measured by an NDJ-8s rotational viscometer, and the results are shown in Table 1.
TABLE 1
Note: the mass of azodiisobutyronitrile added in test numbers 1-10 is 0.3% of the total mass of the reaction raw materials, and the mass of azodiisobutyronitrile added in test numbers 11 and 12 is 0.5% and 0.1% of the total mass of the reaction raw materials respectively.
As can be seen from the data in table 1, the molar ratio of maleic anhydride to amine compound is 1: the effect is optimal when 2; the fatty amine is preferably selected from the group consisting of tetracosane, dotriacontamine and 1, 24-tetracosane diamine, the fatty alcohol amine is preferably selected from the group consisting of 24-amino-1-tetracosane alcohol, and the number average molecular weight of the quadripolymer is preferably 30000-35000.
Example 2
0.01mol of maleic acid derivative prepared according to test No. 3 in example 1, B2mol of polar vinyl compound B (B for short in the table), C2mol of high-carbon alpha-olefin C (C for short in the table) and d2mol of ethylene are dissolved in petroleum ether (the mass of the reaction raw materials is equivalent), the temperature is raised to 45 ℃ under the protection of nitrogen, after reactants are dissolved and stirred uniformly, benzoyl peroxide accounting for 0.5 percent of the total mass of the reaction raw materials is added, the temperature is raised to 90 ℃ continuously, and after 5 hours of reaction, the solvent is removed by reduced pressure distillation to obtain the tetrapolymer.
Taking 20 parts of the prepared quadripolymer (with the number average molecular weight of 32000-34000), 20 parts of maleate-vinyl acetate-styrene-ethylene copolymer (with the number average molecular weight of 3000) and 5 parts of wax crystal dispersant L2 (namely, wax crystal dispersant L2)
) 8 parts of glycerol and 20 parts of mixed trimethylbenzene are uniformly mixed to prepare the crude oil pour point depressants from #13 to # 31.
Adding the crude oil pour point depressants #13 to #31 prepared in the above steps into Daqing crude oil according to the dosage of 200ppm respectively; the average congealing point and average viscosity of the Daqing crude oil were measured under the same other evaluation conditions as in example 1, and the results are shown in Table 2.
TABLE 2
As can be seen from the data in Table 2, when acrylamide and 1-eicosadiene are preferably selected as other monomers, and the molar ratio of the maleic acid derivative to the acrylamide to the 1-docosadiene to the ethylene is 1:3:1: 20-25, the pour point depressant for crude oil compounded by the quadripolymer synthesized according to the proportion has the best pour point depressing and viscosity reducing effects.
Example 3
30 parts of the tetrapolymer (number average molecular weight of 32000-34000) prepared in test No. 30 of example 2, 5 parts of the maleate-vinyl acetate-styrene-ethylene copolymer (number average molecular weight of 5000), and 15 parts of the wax crystal dispersant L3 (namely, wax crystal dispersant L3)
) 5 parts of a hydrogen bond inhibitor E (abbreviated as E in the table), 3 parts of a drag reducer F (abbreviated as F in the table), 10 parts of a dispersion stabilizer G (abbreviated as G in the table), 8 parts of an emulsifier H (abbreviated as H in the table) and 15 parts of heavy aromatic hydrocarbon are uniformly mixed to prepare crude oil pour point depressants #32 to # 38.
Adding the prepared crude oil pour point depressants #32 to #38 into Daqing crude oil according to the dosage of 400ppm respectively; the average congealing point and average viscosity of the Daqing crude oil were measured under the same other evaluation conditions as in example 1, and the results are shown in Table 3.
TABLE 3
As can be seen from the data in Table 3, the pour point and viscosity reducing effects of the pour point depressant for crude oil are better when pentaerythritol, xylitol or sorbitol is used as a hydrogen bond inhibitor, polyhexadiene is used as a drag reducer, and sorbitan palmitate, sodium dodecyl benzene sulfonate or polyethylene glycol fatty acid ester is used as an emulsifier.
Example 4
H1 parts of the tetrapolymer (number average molecular weight of 32000-34000) prepared in test No. 30 of example 2, h2 parts of the maleate-vinyl acetate-styrene-ethylene copolymer (number average molecular weight of 6000) and h3 parts of the wax crystal dispersant L4 (namely, the wax crystal dispersant L4)
) Sorbitol in h4 parts, polyhexarene in h5 parts, polynaphthalene sodium sulfonate in h6 parts, sodium dodecyl benzene sulfonate in h7 parts and diesel oil in h8 parts are uniformly mixed to prepare crude oil pour point depressants from #39 to # 55.
Adding the prepared crude oil pour point depressants #39 to #55 into Daqing crude oil according to the dosage of 500ppm respectively; the average congealing point and average viscosity of the Daqing crude oil were measured under the same other evaluation conditions as in example 1, and the results are shown in Table 4.
TABLE 4
As can be seen from the data in Table 4, the pour point depressing and viscosity reducing effect of the crude oil pour point depressant containing the tetrapolymer or the maleate-vinyl acetate-styrene-ethylene copolymer is far less than that of the crude oil pour point depressant containing the tetrapolymer or the maleate-vinyl acetate-styrene-ethylene copolymer, which indicates that the tetrapolymer and the maleate-vinyl acetate-styrene-ethylene copolymer have obvious synergistic effect, and in addition, the addition of the drag reducer, the dispersion stabilizer and the emulsifier also obviously contributes to the improvement of the pour point depressing and viscosity reducing effect of the product, wherein the pour point depressing and viscosity reducing effect of the crude oil pour point depressant #46 is optimal.
Example 5
The pour point depressant #13 for crude oil in example 2 and the pour point depressants #40, #48 and #54 for crude oil in example 4 were added to Daqing crude oil and Liaohe thick oil at a dosage of 500ppm, wherein the pour point of the Liaohe thick oil was 26 ℃ and the apparent viscosity was 6500mPa · s (25 ℃), and the pour point and viscosity reducing effects of the pour point depressants for crude oil of HCC type from Suzhou Hechuan chemical technology, Inc. were used as comparative data. The other evaluation conditions were the same as in example 1, and the average condensation point and the average viscosity of Daqing crude oil and Liaohe thick oil were measured, and the results are shown in Table 5.
TABLE 5
As can be seen from the data in Table 5, at the same dosage of 500ppm, the pour point depressant HCC on the market has far lower pour point depressing and viscosity reducing effects on Daqing crude oil and Liaohe thick oil than the crude oil pour point depressant of the invention, and under the condition of increasing the dosage, the pour point depressing effect is equivalent to that of the pour point depressant of the invention, but the viscosity reducing effect is still lower than that of the pour point depressant of the invention. Therefore, the crude oil pour point depressant has good pour point depression and viscosity reduction effects on high-wax crude oil and high-viscosity crude oil, and has a remarkable promotion effect on the exploitation and transportation of the crude oil.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A tetrapolymer for use in the pour point depression of crude oil, comprising structural units derived from:
a maleic acid derivative;
a polar vinyl compound;
high carbon alpha-olefins; and
ethylene;
the molar ratio of the maleic acid derivative, the polar vinyl compound, the high-carbon alpha-olefin and the ethylene is 1: 1-5: 1-2: 10-30;
the maleic acid derivative is obtained by amidating maleic anhydride and an amine compound, wherein the amine compound is one of tetracosane, dotriacontamine, 1, 24-tetracosane diamine and 24-amino-1-tetracosanol;
the polar vinyl compound is selected from one of acrylic acid, acrylamide, acrylic sulfonic acid, sodium allylsulfonate, p-styrene sulfonic acid and sodium p-styrene sulfonate;
the high-carbon alpha-olefin is selected from one of 1-eicosene, 1-eicosadiene, 1-tetracosene and 1-dioctadecene.
2. The tetrapolymer of claim 1, wherein the tetrapolymer has a number average molecular weight of 5000 to 100000.
3. A process for the preparation of a tetrapolymer according to claim 1 or 2, comprising the steps of:
and (3) carrying out copolymerization reaction on the maleic acid derivative, the polar vinyl compound, the high-carbon alpha-olefin and the ethylene to obtain the quadripolymer.
4. The method of preparing a tetrapolymer according to claim 3, wherein the maleic acid derivative is prepared by the steps of:
dissolving the maleic anhydride and the amine compound in a solvent, heating to 45-50 ℃, adding a catalyst, continuously heating to 90-130 ℃, and carrying out amidation reaction for 2-8 hours to obtain the maleic acid derivative.
5. The method of claim 3, wherein the copolymerization of the maleic acid derivative, the polar vinyl compound, the high-carbon α -olefin, and the ethylene to obtain the tetrapolymer comprises:
dissolving the maleic acid derivative, the polar vinyl compound, the high-carbon alpha-olefin and the ethylene in a solvent, heating to 45-50 ℃ under a protective atmosphere, adding an initiator, continuously heating to 75-100 ℃, reacting for 3-10 hours, and desolventizing to obtain the quadripolymer.
6. The method of preparing a tetrapolymer according to claim 5, wherein the initiator is at least one selected from the group consisting of diisopropyl peroxydicarbonate, dibenzoyl peroxide, azobisisobutyronitrile, di-t-butyl peroxide, cumene hydroperoxide and cyclohexanone peroxide, and the mass of the initiator is 0.1 to 1% of the total mass of the maleic acid derivative, the polar vinyl compound, the high carbon α -olefin and the ethylene.
7. Use of a tetrapolymer according to claim 1 or 2 for the pour point depression of crude oil.
8. The pour point depressant for crude oil is characterized by comprising the following components in parts by mass:
9. the crude oil pour point depressant of claim 8,
the number average molecular weight of the maleic ester-vinyl acetate-styrene-ethylene copolymer is 2000-10000; or
The wax crystal dispersing agent is a polycarboxylic acid derivative; or
The hydrogen bond inhibitor is a polyol; or
The drag reducer is poly alpha-olefin with 8-36 carbon atoms; or
The dispersion stabilizer is selected from lignosulfonate or polynaphthalene sulfonate; or
The emulsifier is at least one selected from sorbitan oleic acid, sorbitan palmitic acid, sodium dodecyl benzene sulfonate, glyceryl stearate, polyoxyethylene lauryl ether, polyoxyethylene cetyl alcohol and polyethylene glycol fatty acid ester.
10. The pour point depressant for crude oil according to claim 9, wherein the polycarboxylic acid derivative is at least one selected from the group consisting of those having the following structures:
the hydrogen bond inhibitor is at least one selected from ethylene glycol, propylene glycol, glycerol, butanediol, pentanediol, hexanediol, pentaerythritol, xylitol and sorbitol;
the dispersion stabilizer is sodium lignosulfonate or sodium polynaphthalene sulfonate.
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