KR101792245B1 - Composition for use in dispersing heavy crude oils containing polyisobutenyl succinic acid-polyamine compound - Google Patents
Composition for use in dispersing heavy crude oils containing polyisobutenyl succinic acid-polyamine compound Download PDFInfo
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- KR101792245B1 KR101792245B1 KR1020150143377A KR20150143377A KR101792245B1 KR 101792245 B1 KR101792245 B1 KR 101792245B1 KR 1020150143377 A KR1020150143377 A KR 1020150143377A KR 20150143377 A KR20150143377 A KR 20150143377A KR 101792245 B1 KR101792245 B1 KR 101792245B1
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
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Abstract
The present invention relates to a composition for heavy oil dispersion comprising a polyisobutenyl succinic acid-polyamine compound. The composition for heavy oil dispersion containing the polyisobutenyl succinic acid-polyamine compound according to the present invention suppresses agglomeration and precipitation of asphaltenes in heavy oil, thereby increasing the dispersion performance and long-term storage performance of heavy oil and reducing incomplete combustion, And can be usefully used as a dispersant for improving the characteristics.
Description
The present invention relates to a composition for heavy oil dispersion comprising a polyisobutenyl succinic acid-polyamine compound.
Petroleum is refined and separated into LPG, naphtha (30 ~ 130 ℃), kerosene (150 ~ 320 ℃), light oil (200 ~ 350 ℃) and residual oil Is used. The residual oil contains heavy oil. Heavy oil is mainly used for diesel engine, boiler heating, and thermal power generation. It is classified into three types, A heavy oil, B heavy oil and C heavy oil depending on specific gravity and viscosity. C heavy oil is a viscous heavy oil which is also called a bunker fuel oil C and is used as a fuel for large boilers and large-size low-speed diesel engines and for combustion devices equipped with preheating and maintaining equipment. In addition, C heavy oil is a mixture of various compounds with different sulfur and chemical structure and molecular weight because of air pollution problem, and consists of compounds such as saturated, aromatic, resin and asphaltene fractions.
Of these compounds, asphaltenes are large in molecular weight and polar, nonvolatile components that are not soluble in light hydrocarbon solvents but are soluble in benzene or toluene solvents. In addition, it is a condensed polyaromatic ring structure containing aliphatic and naphthenic side chains and contains sulfur, oxygen, nitrogen, and the like. Resins, on the other hand, are components that are soluble in hydrocarbon solvents and are insoluble in ethylacetate solvents. They are composed of relatively less aromatic compounds than asphaltenes and have the property of forming complexes with asphaltenes.
As a result, the heavy oil containing asphaltenes has a low carbon burning rate at the time of burning, resulting in an increase in residual carbon content, resulting in incomplete combustion, thereby increasing the generation of soot and dust in the exhaust gas. In addition, since asphaltenes are easily agglomerated, phase separation problems arise. Therefore, it is very difficult to develop an effective method of reducing energy and improving thermal efficiency by suppressing aggregation of asphaltene and generation of sludge in the process of using heavy oil containing asphaltenes and redispersing the generated sludge. It is important.
Recently, various methods such as induction of phase transition by adding changes in temperature, pressure and composition of heavy oil or addition of asphaltene dispersant have been used to prevent aggregation and precipitation of asphaltenes contained in heavy oil. Especially, the asphaltene dispersant is effective to have the properties of Lewis acid because the asphaltene component has the Lewis base property, and it is effective for the aspaltene component to have the effect of preventing pp stacking, hydrogen bonding, acid-base interaction, van der Waals force, Coordination complexes are formed to prevent flocculation and sedimentation.
It has been studied that amphiphilic organic compounds, synthetic inhibitors, alkylphenol polymers, asphaltenes stabilizers and alkylbenzene-derived amphiphiles can be used as the asphaltene dispersant, And it was not possible to obtain great results because of the mixture of various structures.
Accordingly, the present inventors have made efforts to develop a heavy oil dispersant which is more effective than the heavy oil dispersant in the prior art, and the composition for heavy oil dispersion containing the polyisobutenyl succinic acid-polyamine compound according to the present invention is effective for aggregation and precipitation of asphaltenes in heavy oil The dispersibility of the heavy oil and the long-term storage performance are improved, and the present invention has been completed.
An object of the present invention is to provide a composition for heavy oil dispersion comprising a polyisobutenyl succinic acid-polyamine compound.
Another object of the present invention is to provide a composition for heavy oil dispersion comprising a polyisobutenyl succinic acid-polyamine compound and a polyalkyl phenol resin.
In order to achieve the above object,
The present invention relates to a polyisobutenyl succinylamide compound represented by the following formula (1) and a salt thereof; And a polyisobutenylsuccinimide compound represented by the following formula (2):
[Chemical Formula 1]
In Formula 1,
a is an integer from 10 to 100, and b is an integer from 0 to 18;
(2)
In Formula 2,
c is an integer of 10 to 100, and d is an integer of 0 to 18.
The present invention also relates to a polyisobutenyl succinylamide compound represented by the following formula (1) and a salt thereof; A polyisobutenylsuccinimide compound represented by the formula (2); And an alkylphenol resin compound represented by the following formula (3):
[Chemical Formula 1]
In Formula 1,
a is an integer from 10 to 100, and b is an integer from 0 to 18;
(2)
In Formula 2,
c is an integer from 10 to 100, and d is an integer from 0 to 18; And
(3)
In Formula 3,
R 1 are each independently the same or different straight-chain or a C 2- 20 alkyl side chains,
p is an integer from 4 to 35;
The composition for heavy oil dispersion containing the polyisobutenyl succinic acid-polyamine compound according to the present invention can be usefully used as a dispersant for improving dispersion performance and long-term storage performance of heavy oil by suppressing agglomeration and precipitation of asphaltenes in heavy oil.
Further, since the heavy oil containing the composition for heavy oil dispersion according to the present invention has improved dispersibility and improved combustion characteristics, it can be usefully used for marine diesel engines, large-scale low speed diesel engines, large boiler heating, .
BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the composition for heavy oil dispersion of the examples measured by FT-IR. Fig.
Hereinafter, the present invention will be described in detail.
The present invention relates to a polyisobutenyl succinylamide compound represented by the following formula (1) and a salt thereof; And a polyisobutenylsuccinimide compound represented by the following formula (2):
[Chemical Formula 1]
In Formula 1,
a is an integer from 10 to 100, and b is an integer from 0 to 18;
(2)
In Formula 2,
c is an integer of 10 to 100, and d is an integer of 0 to 18.
Hereinafter, each component of the heavy oil dispersion composition will be described in detail.
The composition for heavy oil dispersion according to the present invention forms pp stacking, hydrogen bonding, acid-base interaction, van der Waals force and coordination complex with the asphaltene component so that the asphaltene component flocculates or precipitates The polyisobutenyl succinylamide compound represented by the formula (1) and its salt; And a polyisobutenylsuccinimide compound represented by the general formula (2).
At this time, the polyisobutenyl succinylamide compound represented by Formula 1 and its salt; And the polyisobutenylsuccinimide compound represented by the general formula (2), a and c are the same or different integers, b and d are the same or different integers, more preferably the same integer.
Specifically, the polyisobutenyl succinylamide compound represented by the general formula (1) preferably has a in the range of 10 to 100 and b in the range of 0 to 18; More preferably, a is an integer of 40 to 80 and b is an integer of 0 to 10; It is most preferable that a is an integer of 60 to 70 and b is an integer of 0 to 3.
The salt of the polyisobutenylsuccinylamide represented by the above formula (1) means any salt that can be formed between the carboxylic acid and the amine of the polyisobutenylsulfonylamide represented by the above formula (1) Lt; RTI ID = 0.0 > polyisobutenylsuccinylamide. ≪ / RTI >
Further, the polyisobutenylsuccinimide compound represented by the above formula (2) preferably has an integer of 10 to 100 and an integer of 0 to 18; c is an integer of 40 to 80 and d is an integer of 0 to 10; It is most preferable that c is an integer of 60 to 70 and d is an integer of 0 to 3.
In the composition for heavy oil dispersion according to the present invention, the content of the polyisobutenylsuccinylamide compound represented by Formula 1 is not particularly limited, but the content of the polyisobutenylsuccinimide compound 1 represented by Formula 2 More preferably 0.1 to 2.0 parts by weight, and most preferably 0.1 to 1.7 parts by weight based on 100 parts by weight of the total weight of the composition. If it is contained in an amount of less than 0.01 part by weight, the dispersing effect to the heavy oil tends to decrease. If it exceeds 2.5 parts by weight, the solubility in heavy oil tends to be lowered and precipitates tend to be generated. There is a difficulty in obtaining a composition for heavy oil dispersion containing an amide compound represented by the formula (1), a salt of the amide compound represented by the formula (1) and an imide represented by the formula (2).
Further, in the composition for heavy oil dispersion according to the present invention, the salt content of the polyisobutenylsuccinylamide compound represented by Formula 1 is not particularly limited, but the polyisobutenylsuccinimide compound represented by Formula 2 More preferably 0.1 to 2.0 parts by weight and most preferably 0.3 to 1.4 parts by weight based on 1 part by weight of the total amount of the composition. If it is contained in an amount of less than 0.01 part by weight, there is a problem of reduction in dispersibility of the heavy oil and economical efficiency. If the amount of the compound exceeds 2.5 parts by weight, the solubility of the prepared compound in heavy oil is poor. There is a difficulty in obtaining a composition for heavy oil dispersion containing an amide compound represented by the general formula (1), a salt of the amide compound represented by the general formula (1) and an imide represented by the general formula (2).
The polyisobutenyl succinylamide compound represented by the above formula (1) and its salt of the composition for heavy oil dispersion according to the present invention; And the polyisobutenylsuccinimide compound represented by the formula (2) can be prepared by reacting a polyisobutenylsuccinic acid compound represented by the following formula (4) with a polyamine compound represented by the following formula (5).
[Chemical Formula 4]
M is an integer of 10 to 100;
[Chemical Formula 5]
And n is an integer of 0 to 18.
Specifically, in order to produce the amide compound represented by the formula (1), the salt of the amide compound represented by the formula (1) and the imide compound represented by the formula (2) simultaneously, the polyisobutylene represented by the formula Preferably, m is an integer of 10 to 100, more preferably an integer of 40 to 80, and most preferably an integer of 60 to 70.
In the polyamine compound represented by the general formula (5), n is preferably an integer of 0 to 18; n is more preferably an integer of 0 to 10; It is most preferable that n is an integer of 0 to 3. Examples thereof include diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, and the like.
In order to prepare the amide compound represented by the formula (1), the salt of the amide compound represented by the formula (1) and the imide compound represented by the formula (2) simultaneously at the reaction temperature in the range of 50-200 ° C Reaction temperature in the range of 70-160 DEG C is more preferable, and reaction temperature in the range of 90-140 DEG C is the most preferable.
Furthermore, in order to prepare the amide compound represented by the formula (1), the salt of the amide compound represented by the formula (1) and the imide compound represented by the formula (2) simultaneously, the reaction time in the range of 0.5-6 hours More preferably a reaction time in the range of 1 to 5 hours, and most preferably in the range of 1 to 4 hours.
Accordingly, in the reaction between the compound represented by the general formula (4) and the compound represented by the general formula (5), the formation ratio of the product varies depending on the reaction temperature and the reaction time. And the imide compound represented by the general formula (2) are contained simultaneously in a preferable ratio, the reaction should be carried out by adjusting the reaction temperature and the reaction time within the above-mentioned preferable range. Specifically, The ratio of the product can be controlled by reducing the reaction time when the reaction temperature is high and increasing the reaction time when the reaction temperature is low.
Also, the composition for heavy oil dispersion according to the present invention is a polyisobutenyl succinylamide compound represented by the above formula (1) and a salt thereof; And the polyisobutenylsuccinimide compound represented by the general formula (2) are desirably contained at the same time in an appropriate ratio. Therefore, a method of controlling the equivalence of the polyisobutenylsuccinic acid compound represented by the general formula (4) and the polyamine compound represented by the general formula .
Specifically, the polyamine compound represented by the formula (5) is preferably used in an amount of 0.01 to 1.5 equivalents, more preferably 0.1 to 1.0 equivalents, relative to 1 equivalent of the polyisobutenyl succinic acid compound represented by the formula (4) , And most preferably 0.6 to 0.8 equivalents. When the amount of the polyamine compound is less than 0.01 equivalents, there is a problem that a product in which a large number of polyisobutenyl succinic anhydride is bound to amines at both ends of the polyamine compound is present. When the amount of the polyamine compound exceeds 1.5 parts by weight, Or the production of the polyisobutenylsuccinylamide compound represented by the general formula (1) is increased. Therefore, the present invention provides an amide compound represented by the general formula (1), a salt of the amide compound represented by the general formula (1) It is difficult to obtain a mixture of the imide compound represented by the formula
Furthermore, the composition for heavy oil dispersion according to the present invention comprises the polyisobutenylsuccinylamide compound represented by Formula 1 and its salt; And the polyisobutenylsuccinimide compound represented by the general formula (2) can be used in the form of an admixture or a mixture of commonly commercially available compounds in the optimum mixing range of the intended dispersing effect of the present invention.
The composition for heavy oil dispersion according to the present invention comprises the polyisobutenyl succinylamide compound represented by the above formula (1) and its salt as described above; And the polyisobutenylsuccinimide compound represented by the general formula (2) simultaneously, the dispersion of the heavy oil is effectively improved as compared with the case of containing at least one of the compound represented by the formula (1) and the salt thereof and the compound represented by the formula (See Experimental Example 2 and Table 2 below).
Therefore, the heavy oil-dispersible composition according to the present invention has excellent dispersibility, thereby suppressing cohesion and precipitation of asphaltenes in heavy oil, thereby increasing the dispersion performance and long-term storage performance of heavy oil, The heavy oil containing the composition can be usefully used for marine diesel engines, large-size low-speed diesel engines, large boiler heating, thermal power generation fuels and the like because of improved dispersibility and improved combustion characteristics.
The present invention also relates to a polyisobutenyl succinylamide compound represented by the following formula (1) and a salt thereof; A polyisobutenylsuccinimide compound represented by the formula (2); And an alkylphenol resin compound represented by the following formula (3):
[Chemical Formula 1]
In Formula 1,
a is an integer from 10 to 100, and b is an integer from 0 to 18;
(2)
In Formula 2,
c is an integer from 10 to 100, and d is an integer from 0 to 18; And
(3)
In Formula 3,
R 1 are each independently the same or different straight-chain or a C 2- 20 alkyl side chains,
p is an integer from 4 to 35;
Hereinafter, each component of the heavy oil dispersion composition will be described in detail.
The composition for heavy oil dispersion according to the present invention forms pp stacking, hydrogen bonding, acid-base interaction, van der Waals force and coordination complex with the asphaltene component so that the asphaltene component flocculates or precipitates The polyisobutenylsuccinylamide compound represented by Formula 1 and its salt; A polyisobutenylsuccinimide compound represented by the formula (2); And the alkylphenol resin compound represented by the general formula (3).
Here, the polyisobutenyl succinyl amide compound represented by Formula 1 and its salt; Or the polyisobutenylsuccinyl imide compound represented by the formula (2) is as described above.
Furthermore, an alkylphenol resin compound represented by the formula (3) is preferably a substituent of R 1 in the phenol monomer are each independently the same or different straight-chain or a C 2- 20 alkyl side chain, and each independently represent the same or different straight-chain or more preferably C 4- 15 alkyl side chain, and each independently more preferably the same or different straight-chain or branched butyl (C 4 alkyl) or hexadecyl (C 10 alkyl). That is, a butylphenol resin or a decylphenol resin is preferable.
Here, the alkylphenol resin compound represented by Formula 3 prevents the materials dispersed in the heavy oil from being precipitated through packing.
In the composition for heavy oil dispersion according to the present invention, the content of the polyisobutenylsuccinylamide compound represented by Formula 1 is not particularly limited, but the content of the polyisobutenylsuccinimide compound 1 represented by Formula 2 More preferably 0.1 to 2.0 parts by weight, and most preferably 0.1 to 1.7 parts by weight based on 100 parts by weight of the total weight of the composition. If it is contained in an amount of less than 0.01 part by weight, the dispersing effect to the heavy oil tends to decrease. If it exceeds 2.5 parts by weight, the solubility in heavy oil tends to be lowered and precipitates tend to be generated. There is a difficulty in obtaining a composition for heavy oil dispersion comprising an amide compound represented by the formula (1), a salt of the amide compound represented by the formula (1), an imide represented by the formula (2) and an alkylphenol resin represented by the formula (3).
Further, in the composition for heavy oil dispersion according to the present invention, the salt content of the polyisobutenylsuccinylamide compound represented by Formula 1 is not particularly limited, but the polyisobutenylsuccinimide compound represented by Formula 2 More preferably 0.1 to 2.0 parts by weight and most preferably 0.3 to 1.4 parts by weight based on 1 part by weight of the total amount of the composition. If it is contained in an amount of less than 0.01 part by weight, there is a problem of reduction in dispersibility of the heavy oil and economical efficiency. If the amount of the compound exceeds 2.5 parts by weight, the solubility of the prepared compound in heavy oil is poor. , An amide compound represented by the formula (1), a salt of the amide compound represented by the formula (1), an imide represented by the formula (2) and an alkylphenol resin represented by the formula (3).
In the composition for heavy oil dispersion according to the present invention, the content of the alkylphenol resin compound represented by the formula (3) is not particularly limited, but the amide compound represented by the formula (1), the amide compound represented by the formula The amount of the salt and the imide compound represented by Formula 2 is preferably 0.01 to 1.0 part by weight, more preferably 0.01 to 0.5 part by weight, and more preferably 0.05 to 0.3 part by weight, based on 1 part by weight of the total amount of the imide compound It is most preferred to include. The amount of the amide compound represented by the formula (1), the salt of the amide compound represented by the formula (1) and the salt of the amide compound represented by the formula (2) There is a difficulty in obtaining a composition for heavy oil dispersion comprising an imide and an alkylphenol resin represented by the general formula (3).
Further, in the composition for heavy oil dispersion according to the present invention, the alkylphenol resin compound represented by Formula 3 may be prepared by condensation reaction of a commercially known alkylphenol and formaldehyde compound, or a commercially available compound Can be mixed and used in an optimum mixing range showing the desired dispersing effect.
The alkylphenol resin compounds represented by the above formula (3) are preferably used by mixing different types of alkylphenol resins rather than using one kind alone.
The composition for heavy oil dispersion according to the present invention comprises the polyisobutenyl succinylamide and the salt thereof represented by the formula (1) as described above; A polyisobutenylsuccinimide compound represented by the formula (2); And the alkylphenol resin compound represented by the formula (3), thereby to obtain a compound represented by the formula (1) and a salt thereof; And the compound represented by the general formula (2) alone, or when the alkylphenol resin represented by the general formula (3) is contained singly, the dispersion of the heavy oil is effectively improved 2 and Table 3).
Therefore, the heavy oil-dispersible composition according to the present invention has excellent dispersibility, thereby suppressing cohesion and precipitation of asphaltenes in heavy oil, thereby increasing the dispersion performance and long-term storage performance of heavy oil, The heavy oil containing the composition can be usefully used for marine diesel engines, large-size low-speed diesel engines, large boiler heating, thermal power generation fuels and the like because of improved dispersibility and improved combustion characteristics.
The composition for heavy oil dispersion is preferably used in an amount of 10-500 ppm ((g / g%) / 10000) based on 100 parts by weight of the heavy oil with respect to the heavy oil, more preferably 30-300 ppm, -200 ppm is most preferable.
Furthermore, the composition for heavy oil dispersion according to the present invention may further contain additives insofar as the effect of the present invention does not improve the intended effect, in order to achieve a different effect from the intended effect of the present invention. The additive may further include organic solvents, metal deactivators, antioxidants, antiwear agents, corrosion inhibitors, scuffing inhibitors, extreme pressure agents, foam inhibitors, anti-emulsifiers, friction modifiers, pour point depressants, .
Hereinafter, the additive will be described in detail.
As the organic solvent, a paraffinic oil is preferably used, and it is more preferable to use a material modified by hydrotreating or dewaxing. The paraffinic oil modified by the hydrotreating or dewaxing treatment is a hydrotreated heavy paraffinic distillate (CAS Registration No. 64742-54-7) or a hydrotreated paraffinic distillate ( Hydrotreated light paraffinic distillate (CAS Registration No. 64742-55-8), Solvent-dewaxed heavy paraffinic distillate (CAS Registration No. 64742-65-0), Solvent-Dewaxed paraffin distillate Solvent-dewaxed light paraffinic distillate (CAS registration number 64742-56-9), hydrotreated and dewaxed heavy paraffinic distillate (CAS registration number 91995-39-0), and hydrotreated and dewaxed At least one selected from the group consisting of hydrotreated and dewaxed light paraffinic distillate (CAS Registration No. 91995-40-3), but is not limited thereto.
The content of the organic solvent may be in the range of 5 to 100 parts by weight based on 100 parts by weight of the total weight of the composition for heavy oil dispersion, considering the effect of reducing the flash point and the kinematic viscosity, minimizing the generation of dust and residual carbon content, More preferably 7 to 13 parts by weight, most preferably 8 to 12 parts by weight.
Examples of the metal deactivator include derivatives of benzotriazole, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, 2-alkyldithiobenzothiazole, 2- (N, Dialkyldithiocarbamoyl) benzothiazole, 2,5-bis (alkyl-dithio) -1,3,4-thiadiazole, 2,5-bis (N, Carbamoyl) -1,3,4-thiadiazole, 2-alkyldithio-5-mercaptothiadiazole, and the like.
Furthermore, the antioxidants include diphenylamine, hindered phenol, molybdenum dithiocarbamate, vulcanized olefin, and mixtures thereof. The antioxidant may also be an aromatic amine, an alkylated diphenylamine, a vulcanized olefin such as a sulfide or a bifluoride or a mixture thereof; And molybdenum compounds. It can also act as an anti-wear agent.
Examples of the corrosion inhibitor include an amine salt of a carboxylic acid such as octylamine octanoate, dodecenylsuccinic acid or anhydride and a condensation product of a fatty acid such as oleic acid and a polyamine, and a polyglycol, And esters of alkenyl succinic acid having an alkenyl group containing from 2 to 24 carbon atoms.
Further, the anti-scuffing agent may be an organic sulfide, a polysulfide such as benzyl disulfide, bis- (chlorobenzyl) disulfide, dibutyl tetrasulfide, di-tert-butyl polysulfide, vulcanized sperm oil, Vulcanized diphenylenes, vulcanized terpenes, vulcanized diels-elder addition products, alkylsulphenyl N'N-dialkyldithiocarbamates, reaction products of polybasic acid esters and polyamines, 2,3 - chlorobutyl ester of dibromopropoxyisobutyric acid, acetoxymethyl ester of dialkyldithiocarbamic acid, acyloxyalkyl ether of xanthogen, and mixtures thereof.
Examples of such extreme pressure (EP) agents include oil soluble sulfur-containing and chlorosulfur-containing EP agents, chlorinated hydrocarbon EP agents and phosphorus EP agents, and foam inhibitors include organosilicones such as polyacetates, dimethylsilicols, polysiloxanes, Polyacrylates or mixtures thereof. Examples of the foam inhibitor include silicone, polyethyl acrylate, a copolymer of ethyl acrylate and 2-ethylhexyl acrylate, and a copolymer of ethyl acrylate, 2-ethylhexyl acrylate and polyvinyl acetate.
Further, the above-mentioned anti-emulsifier includes a derivative of propylene oxide, a derivative of ethylene oxide, a polyoxyalkylene alcohol, an alkylamine, an amino alcohol, a diamine or a polyamine reacted with ethylene oxide or a substituted ethylene oxide or a mixture thereof . Examples of the anti-emulsifier include trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides, (ethylene oxide-propylene oxide) polymers, and mixtures thereof.
The friction modifier may also include fatty amines and esters such as glycerol esters such as glycerol monooleate, borated glycerol esters, fatty phosphites, fatty acid amides, fatty epoxides, borated fatty epoxides, alkoxylated Fatty amines, borated alkoxylated fatty amines, metal salts of fatty acids, vulcanized olefins, fatty imidazolines, condensation products of carboxylic acids and polyalkylene-polyamines, and amine salts of alkylphosphoric acids.
Furthermore, the pour point reducing agent may be an ester of maleic anhydride-styrene copolymer; Polymethacrylate; Polyacrylates; Polyacrylamide; A condensation product of a halo paraffin wax and an aromatic compound; Vinyl carboxylate polymers; And dialkyl fumarate, vinyl esters of fatty acids, ethylene-vinyl acetate copolymers, alkyl vinyl ethers, and mixtures thereof.
Hereinafter, the present invention will be described in detail with reference to Examples and Experimental Examples.
However, the following examples and experimental examples are illustrative of the present invention, and the contents of the present invention are not limited thereto.
< Manufacturing example 1> Polyisobutenyl Preparation of anhydrous succinic acid
Polyisobutenyl succinic anhydride can be prepared by methods known in the art. Specifically, polyisobutene (100 g, 0.1 mol) having a number average molecular weight of 1000 and maleic anhydride (9.8 g) were placed in a high-pressure reactor and subjected to an Alder-ene reaction at 200 ° C. for 6 hours, A hydrocarbon solvent (150 mL) was added and the carbonized component was filtered to obtain polyisobutenylsuccinic anhydride (97% yield).
< Example 1 > Polyisobutenyl Succino Amide And salts thereof, or Succino The composition for heavy oil dispersion 1 containing imide
The polyisobutenyl succinic acid compound (10 g) obtained in Preparation Example 1 was added to ethyl acetate (20 mL), and the temperature was raised to 90 ° C to dissolve the solution transparently. Ethylenediamine (0.25 g) was added to the solution and reacted for 1 hour to obtain the desired compound. At this time, the total acid number (TAN) of the dispersant is 18.4 mgKOH / g and the total base number (TBN) is 9.7 mgKOH / g.
< Example 2> Of polyisobutenyl Succino Amide And salts thereof, or Succino The composition for heavy oil dispersion 2 containing imide
The polyisobutenyl succinic acid compound (10 g) obtained in Preparation Example 1 was added to 20 mL of ethyl acetate, and the temperature was raised to 140 캜 to dissolve the solution in a transparent state. Diethylene triamine (0.43 g) was added to the solution and reacted for 4 hours to obtain the target compound. At this time, the total acid number (TAN) of the dispersant is 10.5 mgKOH / g and the total base number (TBN) is 22.9 mgKOH / g.
< Example 3> Of polyisobutenyl Succino Amide And salts thereof, or Succino The composition for heavy oil dispersion 3 containing imide
The polyisobutenyl succinic acid compound (10 g) obtained in Preparation Example 1 was added to 20 mL of ethyl acetate, and the temperature was raised to 140 캜 to dissolve the solution in a transparent state. Triethylenetetramine (0.61 g) was added to the solution and reacted for 1 hour to obtain the desired compound. At this time, the total acid number (TAN) of the dispersant is 14.5 mgKOH / g and the total base number (TBN) is 35.2 mgKOH / g.
< Example 4> Of polyisobutenyl Succino Amide And salts thereof, or Succino A composition for heavy oil dispersion 4 comprising imide
The polyisobutenyl succinic acid compound (10 g) obtained in Preparation Example 1 was added to 20 mL of ethyl acetate, and the temperature was raised to 90 ° C to dissolve the solution in a transparent state. Tetraethylenepentamine (0.79 g) was added to the solution and reacted for 4 hours to obtain the target compound. At this time, the total acid number (TAN) of the dispersant is 11.1 mgKOH / g and the total base number (TBN) is 44.0 mgKOH / g.
< Example 5> Succinylamides of polyisobutenyl and salts thereof, or succinylimides; A composition for heavy oil dispersion comprising an alkylphenol resin
5 parts by weight of an alkylphenol resin mixed with a t-butylphenol resin and a decylphenol resin in a one-to-one ratio (by weight) to 95 parts by weight of the composition of Example 4 was prepared.
< Example 6> succinylamide of polyisobutenyl and its salts, or succinylimide; A composition for heavy oil dispersion comprising an alkyl phenol resin 2
50 parts by weight of the composition of Example 4 was mixed with 50 parts by weight of an alkylphenol resin mixed with a t-butylphenol resin and a decylphenol resin in a one-to-one ratio (weight ratio).
< Example 7> Of polyisobutenyl Succino Amide And salts thereof, or Succino Imide; A composition for heavy oil dispersion comprising an alkylphenol resin 3
Butylphenol resin and decylphenol resin in a ratio of 1: 1 (weight ratio) to 25 parts by weight of an alkylphenol resin mixed with 75 parts by weight of the composition of Example 4 above.
< Comparative Example 1> Polyisobutenyl Succino Amide salt
The polyisobutenyl succinic acid compound (10 g) obtained in Preparation Example 1 was added to ethyl acetate (20 mL), and the temperature was raised to 60 ° C to dissolve the solution transparently. Tetraethylene pentaamine (0.79 g) was added to the solution and reacted for 1 hour to obtain the target compound. At this time, the total acid number (TAN) of the dispersant is 28.8 mgKOH / g and the total base number (TBN) is 58.0 mgKOH / g.
< Comparative Example 2> Polyisobutenyl Succino Amide
The polyisobutenyl succinic acid compound (10 g) obtained in Preparation Example 1 was added to ethyl acetate (20 mL), and the temperature was raised to 60 ° C to dissolve the solution transparently. Tetraethylenepentamine (0.79 g) was added to the solution and reacted for 4 hours to obtain the target compound. At this time, the total acid number (TAN) of the dispersant is 10.5 mgKOH / g and the total base number (TBN) is 43.5 mgKOH / g.
< Comparative Example 3> Polyisobutenyl Succino Imide
The polyisobutenyl succinic acid compound (10 g) obtained in Preparation Example 1 was added to ethyl acetate (20 mL), and the temperature was raised to 90 ° C to dissolve the solution transparently. Tetraethylene pentaamine (0.79 g) was added to the solution, and the temperature was raised to 140 占 폚 and reaction was carried out for 4 hours to obtain the target compound. At this time, the total acid number (TAN) of the dispersant is 1.6 mgKOH / g and the total base number (TBN) is 38.0 mgKOH / g.
< Comparative Example 4> t- Butylphenol Dispersant mixed with resin
The t-butylphenol resin was prepared and used as a commercially known process as follows.
tert-butylphenol (50 g) and oxalic acid (0.5 g) were added to the reactor so that the ratio of t-butylphenol to formaldehyde was 1: 0.7 (mol: mol) An aqueous formaldehyde solution (18 g) was slowly added dropwise over a period of about 1.5-2 hours with caution to the exotherm of the reactor, and further reaction was carried out for 4 hours. After completion of the reaction, distillation under reduced pressure was performed at 200 ° C to remove unreacted monomers and water to obtain the desired compound. The resin thus obtained had a weight average molecular weight of about 1300 g / mol and a softening point of 110 캜.
< Comparative Example 5> Decylphenol Dispersant mixed with resin
The decyl phenol resin was prepared and used as a commercially known process as follows.
Decylphenol (50 g) and oxalic acid (0.5 g) were added to the reactor so that the ratio of decylphenol to formaldehyde was 1: 0.7 (mol: mol), the temperature of the reactor was raised to about 100 캜, and a 37% formaldehyde aqueous solution 12 g) was slowly added dropwise over a period of about 1.5-2 hours with caution to the exotherm of the reactor, and further reaction was carried out for 4 hours. After completion of the reaction, distillation under reduced pressure was carried out at 200 ° C to remove unreacted monomers and water to obtain the target compound. The resin thus obtained had a weight average molecular weight of about 1500 g / mol and a softening point of 100 캜.
< Comparative Example 6> t- Butylphenol Resin and Decylphenol Dispersant mixed with resin
butylphenol resin and a decyl phenol resin were prepared using the t-butylphenol resin prepared in Comparative Example 5 and the decylphenol resin prepared in Comparative Example 6.
50 parts by weight of the t-butylphenol resin prepared in Comparative Example 5 was mixed with 50 parts by weight of the decylphenol resin prepared in Comparative Example 6.
< Experimental Example 1 > Component analysis of the composition for heavy oil dispersion according to the present invention
The following experiments were conducted to analyze the composition of heavy oil dispersion composition and Comparative Examples 1 to 3 according to the present invention.
Specifically, the structure of the synthesized compound was analyzed by FT-IR (FTS165, Bio-Rad), and the polyisobutenyl ansuccinic acid compound represented by the formula (4) was subjected to a ring-opening reaction with the polyamine compound represented by the formula a carbonyl group in the acid ring carbonyl peak (v 1789 and 1866 cm - 1) disappears, and the amide carbonyl peak (1640 cm -1 v large), the salt of the amide carbonyl peak (1500 cm -1 v large) of the product And an imide carbonyl peak (v 1700 cm -1 ) were observed and analyzed.
Based on the experimental results measured by the above method, each amide and its salt, based on the functional group 隆 CH 2 , represented by the polyisobutenylsuccinyl-polyamine compound (amide and its salt; and imide); And the imide ratio were calculated by the following formula 1, and the results are shown in the following Table 1 and FIG.
[Equation 1]
Wherein Aah is the range of the polyisobutenyl anhydridesuccinate compound; ARr is the reference range of reactants; ARp is the reference range of the product; Al is the range of the imide; Aam is a range of amides; And As: amide salts.
(%)
< Experimental Example 2> Heavy oil Dispersibility evaluation
In order to examine the dispersibility of the heavy oil dispersion compositions of Examples 1 to 7 and Comparative Examples 1 to 7 according to the present invention, the following experiment was conducted.
Specifically, heavy oil having a sulfur content of 1% was prepared in a separate vessel and heated to 60 ° C. The heavy oil dispersion compositions of Examples 1 to 7 and Comparative Examples 1 to 7 were added to each of the heated heavy oils so as to have the same concentration (50 to 200 ppm), followed by stirring. After stirring, 1 g of the sample was diluted with 9 g of toluene, stirred for 30 minutes, taken 2 mL, mixed with 23 mL of heptane, and stirred for 5 minutes. The solution was placed in a turbiscan tube (vial) and scanned every minute. The initial dispersion index for 15 minutes and the dispersion index after 3, 6, 24, 48, and 72 hours were measured using a Turbiscan LA b Model instrument according to ASTM D7061-04 Analysis method. The dispersion performance was calculated from the following equation (2), and the results are shown in Tables 2 and 3 below. ≪ tb > < TABLE >
&Quot; (2) "
Here, S is a variance index (standard deviation on deta T (t)); X i is the average transmittance for each 60 seconds; The average of X T = X i (X T = X 1 + X 2 ... + X 16/16); And n is the number of repeated analysis sets (16 in this analysis).
Table 2 below shows the dispersion indexes of Examples 1 to 4 and Comparative Examples 1 to 3 according to measurement time.
(blank)
As shown in Table 2, the polyisobutenyl succinylamide compounds and the salts thereof according to the present invention; (Examples 1 to 4) comprising a mixture of a polyisobutenylsuccinimide compound and a polyisobutenylsuccinimide compound were mixed together in the same manner as in Example 1 except that the salt of the polyisobutenylsuccinylamide compound was used alone (Comparative Example 1) (Comparative Example 2) exhibited a significantly lower dispersion index than the case where the polyisobutenylsuccinimide compound was used alone (Comparative Example 3). In particular, it was found that the composition for heavy oil dispersion of Example 4 prepared using tetraethylene pentaimine exhibited a significantly lower dispersion index than Comparative Examples 1 to 3.
Table 3 shows the dispersion indexes of Examples 4 to 7 and Comparative Examples 4 to 6 according to measurement time.
(blank)
4
6
Exclusive
Exclusive
ratio
ratio
In Table 3,
C4 is a t-butylphenol resin, C10 is a decylphenol resin, and C4 and C10 are a mixture of t-butylphenol resin and decylphenol resin (1: 1, weight ratio).
As shown in Table 3, the polyisobutenylsuccinylamide compounds and the salts thereof according to the present invention according to the present invention; (Examples 5 to 7) comprising a polyisobutenylsuccinimide compound and an alkylphenol resin compound (Examples 5 to 7) exhibited significantly lower dispersion indexes than the case where only alkylphenol resin was used (Comparative Examples 4 to 6) Respectively. Particularly, the composition for heavy oil dispersion according to the present invention further comprises an alkylphenol resin in which a t-butylphenol resin and a decylphenol resin (1: 1, weight ratio) are mixed together so that the t-butylphenol resin or the decylphenol resin alone And the dispersion index was significantly lower than that in the case of using.
Accordingly, it can be seen that the composition for heavy oil dispersion according to the present invention remarkably improves dispersion performance and long-term storage performance of heavy oil by suppressing agglomeration and precipitation of asphaltenes in heavy oil.
Claims (16)
A salt of a polyisobutenyl succinylamide compound represented by the following formula (1); And
1. A composition for heavy oil dispersion comprising a polyisobutenylsuccinimide compound represented by the following formula (2)
Wherein the salt of the polyisobutenyl succinyl imide compound, the polyisobutenyl succinylamide compound and the polyisobutenyl succinylamide compound is contained in a weight ratio of 1: 0.24-0.49: 0.35-0.73:
[Chemical Formula 1]
(In the formula 1,
a is an integer from 10 to 100, and b is an integer from 0 to 18; And
(2)
(In the formula (2)
c is an integer of 10 to 100, and d is an integer of 0 to 18).
[Chemical Formula 4]
(Wherein m is an integer of 10 to 100);
[Chemical Formula 5]
(Wherein n is an integer of 0 to 18).
A salt of a polyisobutenyl succinylamide compound represented by the following formula (1);
A polyisobutenylsuccinimide compound represented by the following formula (2); And
Butyl phenol resin and decyl phenol resin in an amount of 1: 1 by weight,
Wherein the salt of the polyisobutenyl succinyl imide compound, the polyisobutenyl succinylamide compound and the polyisobutenyl succinylamide compound is contained in a weight ratio of 1: 0.24-0.49: 0.35-0.73,
The alkylphenol resin may be,
And 5 parts by weight based on 95 parts by weight of the total weight of the polyisobutenyl succinyl imide compound, the polyisobutenyl succinyl amide compound and the polyisobutenyl succinylamide compound.
[Chemical Formula 1]
(In the formula 1,
a is an integer from 10 to 100, and b is an integer from 0 to 18; And
(2)
(In the formula (2)
c is an integer of 10 to 100, and d is an integer of 0 to 18).
Wherein the dispersant disperses heavy asphaltenes.
Wherein the heavy oil is dispersed in asphaltenes.
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