CA2708416C - Ionic liquids as viscosity reducers of heavy crude oils - Google Patents
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Abstract
This invention relates to the application of ionic liquids in reducing the viscosity of crude with API grade values between 10 and 20. These ionic liquids consist of cations of type imidazolium, pyridinium, isoquinolinium and ammonium, which have aliphatic and aromatic substituent, and various anions from the following:
R4COO-, CI-, Br-, [BF4]-, [PF6]-, [SbF6]-, [AlCl4]-, [R5SO4]-, [N(OTf)2]-, [CF3CO2]-, [CF3SO3]-, [N(CN)2]-, [OTs]-, [SCN]-, [lnCl4]-, [FeCI4]-, where R4 is represented by alkyl, cycloalkyl, benzyl, alkenyl, functionalized aromatic or alkyl, from 1 to 18 carbon atoms chains, R5 is represented by methyl (CH3- ) and ethyl (CH3CH2-).
R4COO-, CI-, Br-, [BF4]-, [PF6]-, [SbF6]-, [AlCl4]-, [R5SO4]-, [N(OTf)2]-, [CF3CO2]-, [CF3SO3]-, [N(CN)2]-, [OTs]-, [SCN]-, [lnCl4]-, [FeCI4]-, where R4 is represented by alkyl, cycloalkyl, benzyl, alkenyl, functionalized aromatic or alkyl, from 1 to 18 carbon atoms chains, R5 is represented by methyl (CH3- ) and ethyl (CH3CH2-).
Description
IONIC LIQUIDS AS VISCOSITY REDUCERS
OF HEAVY CRUDE OILS
DESCRIPTION
TECHNICAL FIELD OF THE INVENTION
The present invention is related to the application of ionic liquids to reduce the viscosity of crude oils with API grades between the ranges 10 to 20.
Specifically, the objective of the invention is related to the application as viscosity reducers of different families of ionic liquids of general formula CPA-, where C+
represents a organic cation, specifically but not exclusively, of the kinds:
alkyl-pyridinium, di-alkyl imidazolium, trialkyl imidazolium, tetraalkyl ammonium, alkyl quinolinium; while the anion A- is represented by: R4C00-, CI-, Br, [BEd-, [PF6J-, [SbF6]-, [A1C14]-, [R6S041-, [N(OT02]-, [CF3CO2]-, [CF3S03]-, [N(CN)2]-, [OTs], [SCN], [InCla], [FeCI4]-.
BACKGROUND OF THE INVENTION
Globally, the oil industry faces the problem of transporting crude oils with lower API
degrees, and for the case of Mexico, this represent the majority of crude oil extracted and those who are proven reserves, whose viscosity are within the range of 103 to 106 cP at 25 C. Conventional transportation of very viscous crude oil from production sites to refineries is not economically feasible, it is estimated that a crude, the desired value of around 200 cP viscosity.
Different solutions have been developed for the transportation of the heavy and ultra heavy crude oil such as: light crude oil dilution or dilution with other stream light, water injection, oil and pipes preheating, adding of flow improvers. However, each method has technical, logistical and economical disadvantages [Williams B., Oil and Gas J(1984) 1245].
The flow improvers are mostly copolymers such as: highly branched polyolefins ethylene-vinyl acetate, ethylene-vinyl esters, styrene maleic anhydride, fatty amides, acrylates [Machado Andre L. C. et al, J. Petrol. Sc!. Eng. (2001) 32 159].
Ionic liquids are chemical compounds that have received attention for its potential to be used in different branches of industry, especially for possessing physicochemical properties such as negligible vapor pressure, non-flammable, non-corrosive and have low toxicity, making them excellent substitutes for common organic solvents [Wasserscheid P., Keim W. (Eds.), Ionic Liquids in Synthesis, Wiley-VCH, Wenheim, 2004; Welton, T., Chem. Rev. (1999) 99, 2071; Zhao H., Malhotra S. V., Aldrichimica Acta (2002) 35 75], which has promoted its application in different processes of oil refining and chemical industry [Rogers, R. D.; Seddon, K. R., (Eds.), Ionic Liquids:
Industrial Applications of Green Chemistry. ACS, Boston, (2002); Rogers R. D.;
Seddon K. R. (Eds.), Ionic Liquids as Green Solvent: Progress and Prospects.
(ACS
Symposium Series), Boston (2003); Rogers R. D.; Seddon K. R., (Eds.) Ionic Liquids IIIB: Fundamentals, Progress, Challenges, and Opportunities: Transformations and Processes (ACS Symposium Series), Boston, (2005); Roger, R. D.; Seddon, K. R.;
Volkov, S. (Eds.) Green Industrial Applications of Ionic Liquids. (NATO
Science Series),Kluwer Academic Publishers, Dordrecht, Netherlands (2002)]. Next are some examples:
1. Dicationic ionic liquids that function as lubricants for high temperatures [Canter N., Tribol. Lubr. Technol. (2007) 63 12].
OF HEAVY CRUDE OILS
DESCRIPTION
TECHNICAL FIELD OF THE INVENTION
The present invention is related to the application of ionic liquids to reduce the viscosity of crude oils with API grades between the ranges 10 to 20.
Specifically, the objective of the invention is related to the application as viscosity reducers of different families of ionic liquids of general formula CPA-, where C+
represents a organic cation, specifically but not exclusively, of the kinds:
alkyl-pyridinium, di-alkyl imidazolium, trialkyl imidazolium, tetraalkyl ammonium, alkyl quinolinium; while the anion A- is represented by: R4C00-, CI-, Br, [BEd-, [PF6J-, [SbF6]-, [A1C14]-, [R6S041-, [N(OT02]-, [CF3CO2]-, [CF3S03]-, [N(CN)2]-, [OTs], [SCN], [InCla], [FeCI4]-.
BACKGROUND OF THE INVENTION
Globally, the oil industry faces the problem of transporting crude oils with lower API
degrees, and for the case of Mexico, this represent the majority of crude oil extracted and those who are proven reserves, whose viscosity are within the range of 103 to 106 cP at 25 C. Conventional transportation of very viscous crude oil from production sites to refineries is not economically feasible, it is estimated that a crude, the desired value of around 200 cP viscosity.
Different solutions have been developed for the transportation of the heavy and ultra heavy crude oil such as: light crude oil dilution or dilution with other stream light, water injection, oil and pipes preheating, adding of flow improvers. However, each method has technical, logistical and economical disadvantages [Williams B., Oil and Gas J(1984) 1245].
The flow improvers are mostly copolymers such as: highly branched polyolefins ethylene-vinyl acetate, ethylene-vinyl esters, styrene maleic anhydride, fatty amides, acrylates [Machado Andre L. C. et al, J. Petrol. Sc!. Eng. (2001) 32 159].
Ionic liquids are chemical compounds that have received attention for its potential to be used in different branches of industry, especially for possessing physicochemical properties such as negligible vapor pressure, non-flammable, non-corrosive and have low toxicity, making them excellent substitutes for common organic solvents [Wasserscheid P., Keim W. (Eds.), Ionic Liquids in Synthesis, Wiley-VCH, Wenheim, 2004; Welton, T., Chem. Rev. (1999) 99, 2071; Zhao H., Malhotra S. V., Aldrichimica Acta (2002) 35 75], which has promoted its application in different processes of oil refining and chemical industry [Rogers, R. D.; Seddon, K. R., (Eds.), Ionic Liquids:
Industrial Applications of Green Chemistry. ACS, Boston, (2002); Rogers R. D.;
Seddon K. R. (Eds.), Ionic Liquids as Green Solvent: Progress and Prospects.
(ACS
Symposium Series), Boston (2003); Rogers R. D.; Seddon K. R., (Eds.) Ionic Liquids IIIB: Fundamentals, Progress, Challenges, and Opportunities: Transformations and Processes (ACS Symposium Series), Boston, (2005); Roger, R. D.; Seddon, K. R.;
Volkov, S. (Eds.) Green Industrial Applications of Ionic Liquids. (NATO
Science Series),Kluwer Academic Publishers, Dordrecht, Netherlands (2002)]. Next are some examples:
1. Dicationic ionic liquids that function as lubricants for high temperatures [Canter N., Tribol. Lubr. Technol. (2007) 63 12].
2. As desulphurising agents for gasoline and diesel obtained in the process of oil refining, using ionic liquids of general formula CA, where C+ represents an organic cation, specifically but not exclusively, of a kind: alkyl-pyridinium, di-alkyl imidazolium, trialkyl imidazolium and tetraalkyl ammonium, while A anions are halides of iron Ill, particularly FeC14". [Likhanova N., Martinez R. y Palomeque J., Liquidos ionicos en la desulfuracion de hidrocarburos y procedimiento de obtencion (2008), Patent application, file: MX/a/2008/006731, Folio: MX/E/2008/033527].
3. As desulphurising agents for light naphtha using ionic liquids that are halogen-free and the procedure for the extraction the sulfur compounds with general formula CPA-, where C+ represents an organic cation, specifically but not exclusively, of a kind: alkyl-pyridinium , di-alkyl imidazolium, trialquil imidazolium, tetraalquil ammonium, alkyl-quinolinium, while A" anions are organic carboxylates derived from aliphatic or aromatic carboxylic acids such as acetate, butanoate, stearate, benzoate, among others [Martinez R., Likhanova N., Flores E., and Guzman, D., halogen-free ionic liquids in the desulphurization of gasoline and recovery. (2008), Patent application, File: MX/a/2008/011121, Folio: MX/E/2008/056453].
4. In the extraction of the aromatic compounds in mixtures of aliphatic and aromatic hydrocarbons with ionic liquids constituted in the cationic part by alkyl-imidazolium, alkyl-piridinium, tetraalkyl-ammonium, tetraalkyl-phosphonium, and different anions [Meindersma G. W., Podt A., and De Haan A. B., Fuel Process.
TechnoL (2005) 87 59].
TechnoL (2005) 87 59].
5. In the extraction of nitrogenated compounds in diesel in diesel using 1-butyl-3-methyl-imidazolium chloroaluminate [Peng C., Zubin C., Dezhi Z., Dandong L., and Shuyan Z., Petrol. Sci. TechnoL (2005) 23 1023].
6. In the synthesis of poly-a-olefins (lubricant oils) from 1-octene and 1-decene, using chloroaluminates of alkyl-pyridinium and diethylamomium as catalyst [Ibragimova M. D., Samedova F. I., Casanova R. Z., Azmamedov N. G., and Eivazov E. Z., Synthesis of oligooctene and oligodecene oils in the presence of chloroaluminate ionic liquids, Petrol. Chem. (2007) 47 61].
7. In gasoline desulfurization [Likhanova N, Guzman-Lucero ., Flores E, Garcia P, Dominguez-Aguilar MA, Palomeque J, Martinez-Palou R. Deep Desulfurization of Natural Gasoline using Ionic Liquids. MoL Diversity, in press (1301:
10.1007/s11030-009-9217-x].
Considering the arguments described before, the develop of new alternatives for reducing the viscosity of heavy and ultra-heavy crude oils are required to eliminate the barrier of economic feasibility in the transportation of the heavy oils to the processing centers o shipping, thus, contribute to the integral use of energy resources. Ionic liquids of the present invention represent an effective alternative to the solution of this problem. This is the first time describes the use of ionic liquids such as reducing the viscosity in heavy crude.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is related to the application of different families of ionic liquids in reducing viscosity of heavy crude specifically with the Mexican heavy crude oils included in the range of 10 to 20 API.
Ionic liquids whose application such as reducing the viscosity is claimed in the present invention, were synthesized, purified, and characterized by spectroscopic techniques such as Infrared, Nuclear Magnetic Resonance (1H and 13C) and Mass Espectrometry, according with the methods described in the literature [Bosmann A., Datsevich L., Jess A., Lauter A., Schmit C., Wassercheid P., Chem. Commun.
(2001) 3 2494; Zhang S., Zhang Z., Green Chem. (2001) 4 376; Eller J., Wassercheid P., Jess A., Green Chem. (2001) 6 316; Zhang S., Zhang Q., Conrad Zhang Z., Ind.
Eng.
Chem. Res. (2004) 43 614; Huang C., Chen B., Zhang J., Liu Z., Li Y., Energ.
Fuel (2004) 18 1862].
Ionic liquids object of the present invention, present the general formula C+
A-, where C+ is an organic cation and A- is an organic or inorganic anion, such as is showed in Table 1.
According to one aspect of this disclosure, the particular concentration of each ionic liquid may vary from 0.01% to 0.2% by weight, preferably from 0.01% to 0.1% by weight of such so that the total concentration is between 0.01% and 45% by weight, preferably between 0.05% and 30% by weight, more preferably between 0.08% and 10% by weight and the concentration of inert organic solvents is the difference about 100%.
=
EXAMPLES OF THE INVENTION
Synthesis of ionic liquids General procedure for the synthesis of ionic liquids, without any limitation this represents, this synthesis is based on the methods described in Saravanabubu M., Wiencek J. M., Ren R. X., Linhardt R. J., Carbohydr. Polymer 63 268-271 (2006);
Brindaban C. R., and Subas B., Org. Lett. 7 3049-3052 (2005); Lu L., Cheng S., Gao J., Gao G., and He M. Y., Energy and Fuels 21 383-384 (2007); Hu Y. F., and Guo T.
M., Langmuir 21 8168-8174 (2005); Holbrey J. D., Reichert W. M., Swatlosky R.
P., lo Broker G. A., Pitner W. R., Seddon K. R., and Roger R. D., Green Chem. 4 (2002); Cammarata L., Kazarian S. G., Salter P. A., and Welton T., Phys. Chem.
Chem. Phys. 3 5192-5200 (2001).
1. In the first step, ionic, liquids were synthesized by reacting chlorides and bromides of alkyl, alkenyl, benzyl or alkyl-functionalized organic compounds containing nitrogen atoms as imidazoles, pyridine, isoquinoline and tertiary amines.
2. In the second step anion interchange was carried out using the appropriate compound for exchange, generating a metallic halide, which precipitates and is separated from the reaction by filtration. Both steps were performed using conventional and unconventional energy sources (microwave and ultrasound).
Here an example, although the scope of the present invention is not limited to it.
Table 1. General structure of the cations and anions that are included in the present invention ionic liquids.
C+ (Cationes) Ri (1Ik\N¨R
N
Pyridinium Imidazolium N
Isoquinolinium Ammonium A (Anions) R4c00-, Cr, Br, [BF4i-, [sbF6i-, [Alci4r, ER5so4r, [N(oTo2r, [cF3co2], [cF3so3], [N(cN)2r, [OTs], [SCN], [InCl4r, [FeCI4r where: R, R1, R2 y R3 are independent radicals represented by alkyl, cycloalkyl, benzyl, aromatic, alkenyl or alkyl functionalized chains from 1 to 18 carbon atoms. R4 is represented by alkyl, cycloalkyl, benzyl, alkenyl, aromatic or alkyl functionalized chains from 1 to 18. R5 can be methyl or ethyl.
EXAMPLE
Sythesis of 1-octy1-3-methyl-imidazolium acetate Step 1: In a ball flask provided with magnetic agitation, thermometer, and condenser, 20 mmol of 1-methylimidazole and 60 mmol of 1-bromooctane were mixed. The mixture was heated at 80 C for 24 hours. Two layers are formed when reaction is completed. The upper layer is decanted and the lower phase containing the ionic liquid is washed with ethyl acetate (3 x 20 mL). The solvent was eliminated by reduced pressure.
s Step 2: (Anion interchange): In a round bottomed flask equipped with a magnetic stirring bar, thermometer and reflux condenser, were dissolved 10 mmol of 1-octy1-3-methyl-imidazolium bromide obtained in first step, in 50 mL of acetonitrile.
Ammonium acetate (10mmol) was slowly added to the solution. The mixture was refluxed for 10 hr, and then the precipitate was filtered off, the ionic liquid was dried under vacuum conditions and it was obtained as a yellow liquid.
EVALUATION OF IONIC LIQUIDS AS VISCOSITY REDUCERS
Dissolutions of ionic liquids were prepared either from a single ionic liquid or from a combination of several ionic liquids, in which their total concentrations were between is 0.01% and 45% by weight, preferably within 0.05% to 30% by weight, using inert organic solvents whose boiling points are within 70-210 C; preferably acetonitrile, dimethylformamide, branched and linear aliphatic alcohols containing 3-10 carbon atoms such as isopropanol, butanol, pentanol and aromatic solvents such as benzene, toluene, xylenes, as well as mixtures of them. Once having prepared the concentrated dissolutions, were added aliquots of single ionic liquid dissolution or combinations of them to the oil samples whose API gravity between 10 and 20, for which as an example that does not represent any limitation, raw samples of 50 to 500 mL, preferably 80 to 300 mL, was added to 2-50 mL, preferably from 2 to 25 mL
of solutions of ionic liquids. Then, was stirred continuously in a temperature, , range between 15 and 25 =ik C, and a pressure between 585 and 70 milt during a Period of time between Z.and 8 hours, and finally, were determined the viscosity of ,samples of crude which was added a solution of ionic liquids, also the same procedure was performed by adding solvents to the oil only and in this case, it was noted that the viscosity of crude did not change.
, , Table 2. Determination of dynamic viscosity (D. Visc.) of heavy crude with ionic liquid's (IL) addition (1000 ppm) using a viscometer SVM 3000 Anton Paar Staubinger Structure of IL D. Visc., % of p g/cm3, API, (1000 ppm) 40 C, cP reduction 40 C 20 C
Et IC2-Ph Et-NCH - 554.5 5.4 0.9454 15.90 Et CH3C00 Me,/ CH
X-Ph NoN 2- G Ci7H35C00 554.61 5.4 0.9455 15.89 Me 19.-1 CH-Ph Et-N 2 555.42 5.3 0.9453 15.92 Me CH3C00 Bu,NoyNN-CH2-Ph e CH3C00 561.91 4.2 0.9451 15.95 Me--NON-CH2-Ph CH3C00 e 567.61 3.2 0.9456 15.87 Me Ig_CH
Et- 2PhN -- 568.48 3.1 0.9454 15.90 I
Me PhC00 Ph-H2C,.NN-CH2-Ph G CH3coo 569.10 3.0 0.9457 15.85 Me,N(Z3N-CH2-Ph PF6" 573.0 2.3 0.9456 15.87 Me IC) Et-N-cH2-0Et 577.31 1.6 0.9454 15.90 Me CH3C00 Crude oil without IL's addition: dynamic viscosity: 586.41 cP at 40 C;
Density: 0. 9456 gkm 3 at 40 C; gravity API: 15.87 at 20 C
10.1007/s11030-009-9217-x].
Considering the arguments described before, the develop of new alternatives for reducing the viscosity of heavy and ultra-heavy crude oils are required to eliminate the barrier of economic feasibility in the transportation of the heavy oils to the processing centers o shipping, thus, contribute to the integral use of energy resources. Ionic liquids of the present invention represent an effective alternative to the solution of this problem. This is the first time describes the use of ionic liquids such as reducing the viscosity in heavy crude.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is related to the application of different families of ionic liquids in reducing viscosity of heavy crude specifically with the Mexican heavy crude oils included in the range of 10 to 20 API.
Ionic liquids whose application such as reducing the viscosity is claimed in the present invention, were synthesized, purified, and characterized by spectroscopic techniques such as Infrared, Nuclear Magnetic Resonance (1H and 13C) and Mass Espectrometry, according with the methods described in the literature [Bosmann A., Datsevich L., Jess A., Lauter A., Schmit C., Wassercheid P., Chem. Commun.
(2001) 3 2494; Zhang S., Zhang Z., Green Chem. (2001) 4 376; Eller J., Wassercheid P., Jess A., Green Chem. (2001) 6 316; Zhang S., Zhang Q., Conrad Zhang Z., Ind.
Eng.
Chem. Res. (2004) 43 614; Huang C., Chen B., Zhang J., Liu Z., Li Y., Energ.
Fuel (2004) 18 1862].
Ionic liquids object of the present invention, present the general formula C+
A-, where C+ is an organic cation and A- is an organic or inorganic anion, such as is showed in Table 1.
According to one aspect of this disclosure, the particular concentration of each ionic liquid may vary from 0.01% to 0.2% by weight, preferably from 0.01% to 0.1% by weight of such so that the total concentration is between 0.01% and 45% by weight, preferably between 0.05% and 30% by weight, more preferably between 0.08% and 10% by weight and the concentration of inert organic solvents is the difference about 100%.
=
EXAMPLES OF THE INVENTION
Synthesis of ionic liquids General procedure for the synthesis of ionic liquids, without any limitation this represents, this synthesis is based on the methods described in Saravanabubu M., Wiencek J. M., Ren R. X., Linhardt R. J., Carbohydr. Polymer 63 268-271 (2006);
Brindaban C. R., and Subas B., Org. Lett. 7 3049-3052 (2005); Lu L., Cheng S., Gao J., Gao G., and He M. Y., Energy and Fuels 21 383-384 (2007); Hu Y. F., and Guo T.
M., Langmuir 21 8168-8174 (2005); Holbrey J. D., Reichert W. M., Swatlosky R.
P., lo Broker G. A., Pitner W. R., Seddon K. R., and Roger R. D., Green Chem. 4 (2002); Cammarata L., Kazarian S. G., Salter P. A., and Welton T., Phys. Chem.
Chem. Phys. 3 5192-5200 (2001).
1. In the first step, ionic, liquids were synthesized by reacting chlorides and bromides of alkyl, alkenyl, benzyl or alkyl-functionalized organic compounds containing nitrogen atoms as imidazoles, pyridine, isoquinoline and tertiary amines.
2. In the second step anion interchange was carried out using the appropriate compound for exchange, generating a metallic halide, which precipitates and is separated from the reaction by filtration. Both steps were performed using conventional and unconventional energy sources (microwave and ultrasound).
Here an example, although the scope of the present invention is not limited to it.
Table 1. General structure of the cations and anions that are included in the present invention ionic liquids.
C+ (Cationes) Ri (1Ik\N¨R
N
Pyridinium Imidazolium N
Isoquinolinium Ammonium A (Anions) R4c00-, Cr, Br, [BF4i-, [sbF6i-, [Alci4r, ER5so4r, [N(oTo2r, [cF3co2], [cF3so3], [N(cN)2r, [OTs], [SCN], [InCl4r, [FeCI4r where: R, R1, R2 y R3 are independent radicals represented by alkyl, cycloalkyl, benzyl, aromatic, alkenyl or alkyl functionalized chains from 1 to 18 carbon atoms. R4 is represented by alkyl, cycloalkyl, benzyl, alkenyl, aromatic or alkyl functionalized chains from 1 to 18. R5 can be methyl or ethyl.
EXAMPLE
Sythesis of 1-octy1-3-methyl-imidazolium acetate Step 1: In a ball flask provided with magnetic agitation, thermometer, and condenser, 20 mmol of 1-methylimidazole and 60 mmol of 1-bromooctane were mixed. The mixture was heated at 80 C for 24 hours. Two layers are formed when reaction is completed. The upper layer is decanted and the lower phase containing the ionic liquid is washed with ethyl acetate (3 x 20 mL). The solvent was eliminated by reduced pressure.
s Step 2: (Anion interchange): In a round bottomed flask equipped with a magnetic stirring bar, thermometer and reflux condenser, were dissolved 10 mmol of 1-octy1-3-methyl-imidazolium bromide obtained in first step, in 50 mL of acetonitrile.
Ammonium acetate (10mmol) was slowly added to the solution. The mixture was refluxed for 10 hr, and then the precipitate was filtered off, the ionic liquid was dried under vacuum conditions and it was obtained as a yellow liquid.
EVALUATION OF IONIC LIQUIDS AS VISCOSITY REDUCERS
Dissolutions of ionic liquids were prepared either from a single ionic liquid or from a combination of several ionic liquids, in which their total concentrations were between is 0.01% and 45% by weight, preferably within 0.05% to 30% by weight, using inert organic solvents whose boiling points are within 70-210 C; preferably acetonitrile, dimethylformamide, branched and linear aliphatic alcohols containing 3-10 carbon atoms such as isopropanol, butanol, pentanol and aromatic solvents such as benzene, toluene, xylenes, as well as mixtures of them. Once having prepared the concentrated dissolutions, were added aliquots of single ionic liquid dissolution or combinations of them to the oil samples whose API gravity between 10 and 20, for which as an example that does not represent any limitation, raw samples of 50 to 500 mL, preferably 80 to 300 mL, was added to 2-50 mL, preferably from 2 to 25 mL
of solutions of ionic liquids. Then, was stirred continuously in a temperature, , range between 15 and 25 =ik C, and a pressure between 585 and 70 milt during a Period of time between Z.and 8 hours, and finally, were determined the viscosity of ,samples of crude which was added a solution of ionic liquids, also the same procedure was performed by adding solvents to the oil only and in this case, it was noted that the viscosity of crude did not change.
, , Table 2. Determination of dynamic viscosity (D. Visc.) of heavy crude with ionic liquid's (IL) addition (1000 ppm) using a viscometer SVM 3000 Anton Paar Staubinger Structure of IL D. Visc., % of p g/cm3, API, (1000 ppm) 40 C, cP reduction 40 C 20 C
Et IC2-Ph Et-NCH - 554.5 5.4 0.9454 15.90 Et CH3C00 Me,/ CH
X-Ph NoN 2- G Ci7H35C00 554.61 5.4 0.9455 15.89 Me 19.-1 CH-Ph Et-N 2 555.42 5.3 0.9453 15.92 Me CH3C00 Bu,NoyNN-CH2-Ph e CH3C00 561.91 4.2 0.9451 15.95 Me--NON-CH2-Ph CH3C00 e 567.61 3.2 0.9456 15.87 Me Ig_CH
Et- 2PhN -- 568.48 3.1 0.9454 15.90 I
Me PhC00 Ph-H2C,.NN-CH2-Ph G CH3coo 569.10 3.0 0.9457 15.85 Me,N(Z3N-CH2-Ph PF6" 573.0 2.3 0.9456 15.87 Me IC) Et-N-cH2-0Et 577.31 1.6 0.9454 15.90 Me CH3C00 Crude oil without IL's addition: dynamic viscosity: 586.41 cP at 40 C;
Density: 0. 9456 gkm 3 at 40 C; gravity API: 15.87 at 20 C
8 =
Table 3. Determination of the dynamic viscosity of heavy oil (*API = 15.1) with ionic liquid's (IL) addition (1000 ppm) using a dynamic cut stress (20 sec-1) Me mb CH2-Ph Cl8H37-P4 Me CH3C00 Temperature ( C) Reduction (%) 20 11.5 25 8.5 30 6.5 35 1.7 40 1.0 The results presented in the tables 2 and 3 show that the ionic liquids, which is an object of this invention, reducing oil viscosity
Table 3. Determination of the dynamic viscosity of heavy oil (*API = 15.1) with ionic liquid's (IL) addition (1000 ppm) using a dynamic cut stress (20 sec-1) Me mb CH2-Ph Cl8H37-P4 Me CH3C00 Temperature ( C) Reduction (%) 20 11.5 25 8.5 30 6.5 35 1.7 40 1.0 The results presented in the tables 2 and 3 show that the ionic liquids, which is an object of this invention, reducing oil viscosity
9
Claims (10)
1. The use of ionic liquids formulations to reduce heavy oil viscosity, where the reduction percentage in viscosity is in the range between 1 and 11.5% in heavy crudes that have API gravity from 10 to 20, whether to use a single ionic liquid or combinations thereof or mixtures thereof with solvents, with continuous stirring in a temperature range between 15 and 25°C, and at pressure of 585 to 760 mmHg during a period of 2 to 8 hours.
2. The use of ionic liquid formulations in accordance with claim 1, wherein the particular concentration of each ionic liquid varies from 0.01% to 0.2% by weight, so that the total concentration is between 0.01% and 45% by weight and the concentration of inert organic solvents is the difference up to 100%.
3. The use of formulations of ionic liquids in accordance with claim 1 or 2, where, ionic liquids are included with the general formula C+ A- where C+ is an organic cation and A- is an anion organic or inorganic, and C+ is a cation based imidazolium, pyridinium, isoquinolinium, ammonium (quaternary amine) and derivatives thereof with substituent represented by benzyl, aromatic, cycloalkyl, alkenyl or aliphatic represented by 1 to 18 carbon atoms chains, where in addition A- is an anion organic or inorganic represented by any of the following R4COO-, cr, Br-, [BF4]-, [PF6]-, [SbF6]-,[R5SO4]-, [N(OTf)2]-, [CF3CO2]-, [CF3SO3]-, [N(CN)2]-, [OTs]-, [SCN]-, [InCl4]-, or [FeCl4]-; where R4 is represented by alkyl, cycloalkyl, benzyl, alkenyl, functionalized aromatic or alkyl, from 1 to 18 carbon atoms chains, and R5 is represented by methyl (CH3-) or ethyl (CH3CH2-).
4. The use of ionic liquid formulations in accordance with any one of claims 1 to 3, where, inert organic solvents are used and which boiling point is between 70 and 210°C.
5. The use of ionic liquid formulations in accordance with claim 2, wherein the particular concentration of each ionic liquid varies from 0.01% to 0.1% by weight.
6. The use of ionic liquid formulations in accordance with claim 2, wherein the total concentration is between 0.05% and 30% by weight.
7. The use of ionic liquid formulations in accordance with claim 2, wherein the total concentration is between 0.08% and 10% by weight.
8. The use of ionic liquid formulations in accordance with claim 4, where, the inert organic solvents comprise acetonitrile, dimethylformamide, branched and linear aliphatic alcohols containing at its structure from 3 to 10 carbon atoms, aromatic solvents and/or mixtures thereof.
9. The use of ionic liquid formulations in accordance with claim 8, wherein the aliphatic alcohols comprise isopropanol, butanol, pentanol or mixtures thereof.
10. The use of ionic liquid formulations in accordance with claim 8, wherein the aromatic solvents comprise toluene, benzene, xylenes, or mixtures thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| MXMX/A/2009/007078 | 2009-06-29 | ||
| MX2009007078A MX2009007078A (en) | 2009-06-29 | 2009-06-29 | Ionic liquids as viscosity reducers of heavy crude oils. |
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| Publication Number | Publication Date |
|---|---|
| CA2708416A1 CA2708416A1 (en) | 2010-12-29 |
| CA2708416C true CA2708416C (en) | 2016-10-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2708416A Expired - Fee Related CA2708416C (en) | 2009-06-29 | 2010-06-21 | Ionic liquids as viscosity reducers of heavy crude oils |
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| Country | Link |
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| CA (1) | CA2708416C (en) |
| MX (1) | MX2009007078A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109456270A (en) * | 2018-11-13 | 2019-03-12 | 徐州工程学院 | A kind of ion liquid preparation device |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2729457C (en) | 2011-01-27 | 2013-08-06 | Fort Hills Energy L.P. | Process for integration of paraffinic froth treatment hub and a bitumen ore mining and extraction facility |
| CA2853070C (en) | 2011-02-25 | 2015-12-15 | Fort Hills Energy L.P. | Process for treating high paraffin diluted bitumen |
| CA2931815C (en) | 2011-03-01 | 2020-10-27 | Fort Hills Energy L.P. | Process and unit for solvent recovery from solvent diluted tailings derived from bitumen froth treatment |
| CA2865126C (en) | 2011-03-04 | 2015-12-22 | Fort Hills Energy L.P. | Process for solvent addition to high viscosity bitumen froth |
| CA2735311C (en) | 2011-03-22 | 2013-09-24 | Fort Hills Energy L.P. | Process for direct steam injection heating of oil sands bitumen froth |
| CN102190623B (en) * | 2011-03-25 | 2015-07-01 | 中国纺织科学研究院 | Method for preparing imidazole acetate ionic liquid |
| CA2815785C (en) | 2011-04-15 | 2014-10-21 | Fort Hills Energy L.P. | Heat recovery for bitumen froth treatment plant integration with temperature circulation loop circuits |
| CA3077966C (en) | 2011-04-28 | 2022-11-22 | Fort Hills Energy L.P. | Recovery of solvent from diluted tailings by feeding a solvent diluted tailings to a digester device |
| CA2832269C (en) | 2011-05-18 | 2017-10-17 | Fort Hills Energy L.P. | Temperature control of bitumen froth treatment process with trim heating of solvent streams |
| CN108570315B (en) * | 2017-03-08 | 2020-11-13 | 中国石油化工股份有限公司 | Application of imidazole and/or imidazole derivative, acidified heavy oil viscosity reducer and method for reducing viscosity of acidified heavy oil |
| EP3957704A1 (en) | 2020-08-21 | 2022-02-23 | Vito NV | Method for hydroprocessing an organic compound, and catalysts therefor |
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2009
- 2009-06-29 MX MX2009007078A patent/MX2009007078A/en active IP Right Grant
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2010
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109456270A (en) * | 2018-11-13 | 2019-03-12 | 徐州工程学院 | A kind of ion liquid preparation device |
Also Published As
| Publication number | Publication date |
|---|---|
| MX2009007078A (en) | 2011-01-05 |
| CA2708416A1 (en) | 2010-12-29 |
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