MX2013008554A - Ionic liquids, methylcarbonate-or carboxylates-based, obtaining process and use thereof. - Google Patents

Abstract

The present invention relates to the use of new methylcarbonate-based ionic liquids (Lis) or carboxylates, derived from aliphatic or aromatic carboxylic acids, In the extraction of nitrogen organic or nitrogenous compounds: aliphatic and aromatic, pollutants as hydrocarbon mixture (HCs); through the process of liquid-liquid selective extraction (LI-HCs), at room temperature and atmospheric pressure, where the Lls are immiscible with the HCs, due to the increased affinity for the organic nitrogenous compounds In the middle of LI with regard to the means of HCs In which they are present. This process is performed through a extraction with two phases stirring, followed by a stage of separation, or in a continuous flow system where the nitrogenous compounds are transferred to the phase formed by the LI and as a result the total nitrogen content is substantially reduced In the HCS phase. The new Lls used in the present invention, for the denitrogenation of HCs mixtures, have the general fo rmula C+ A-, where: C+ is a heterocyclic organic cation, or quaternary ammonium-based; and A- is a methylcarbonate- or carboxylates-based anion derived from aliphatic or aromatic carboxylic acids. The main competitive advantages of the novel technology for extraction of the present invention ere: A high efficiency in the elimination of nitrogen compounds mixture of HCs pollutants, Operation conditions of the process, which are substantially soft and environmentally friendly, and substantially reduced costs.

Description

IONIC LIQUIDS, BASE METILCARBONATE O CARBOXYLATES, PROCESS OF OBTAINING AND USE DESCRIPTION TECHNICAL FIELD OF THE INVENTION The present invention relates to novel ionic liquids (Lys) methyl carbonate base or carboxylates derived from aliphatic carboxylic acids or aromatic production process and use in the removal of organic nitrogen compounds or nitrogen: aromatic, aliphatic and contaminants hydrocarbon mixtures (HCs), through a process of selective extraction liquid - liquid (LI-HCs), at room temperature and atmospheric pressure, where the Lys are immiscible with the HCs.

Mixtures of HCs to be denitrogenated by the present invention are preferably petroleum-derived fuels: gasoline, diesel, light cyclic oil and turbosine; as well as other streams of HCs obtained in the oil refining processes.

New Lis of the present invention, used in the denitrogenation mixtures HCs have the general formula C + A "where C * is a heterocyclic organic cation, preferably imidazolium base, pyridinium or isoquinolinium or ammonium based quaternary, more preferably types: tetraalkyl ammonium ^ alkyl pyridinium and alkyl imidazolium, while, A "is methylcarbonate base or carboxylates derived from aromatic aliphatic carboxylic acids or an anion, preferably consisting of substituents of alkyl chains, cicloalquílicas, benzylic, alkenyl, aromatic or functionalized alkyl, of 1 to 18 carbon atoms, such as: butanoate, hexanoate, octanoate and salicylate.

BACKGROUND OF THE I NVENTION Organic nitrogen compounds or nitrogen having an inhibitory effect on the reactions of hydrodesulfurization (HDS), poison expensive catalysts consisting of noble metals for this process, thus significantly difficult to obtain fuels with ultra low sulfur = 15 parts per million (ppm).

The production of fuels, according to the environmental standards of the European Union established for the year 2005, requires reducing the amount of sulfur in diesel and gasoline at levels equal to or lower than 10 ppm. For example, in Germany it was proposed to reduce the amount of sulfur in gasoline and diesel in 2005 to 10 ppm. In the case of the United States of America, the norm for the maximum content of sulfur in gasoline is limited to a maximum of 15 ppm since 2006.

In the case of Mexico, PEMEX Refinación, in line with its commitment to produce and distribute gasoline that complies with environmental legislation under international quality standards, is adjusting its gasoline and diesel production parameters under the Mexican standard NOM-086-Semarnat- Sener-SCFI-2005, which requires a maximum sulfur content in gasoline and diesel from 15 to 30 ppm for the years 2008 to 2010; In the case of Premium gasoline consumed throughout the country, it is on average 30 ppm in weight, with a maximum of 80 ppm, a requirement that is met with the production of Ultra Low Sulfur gasoline (UBA).

In the case of Magna gasoline, the norm indicates that since October 2008, the gasoline consumed in the three main metropolitan areas of the country (Mexico City, Monterrey and Guadalajara), must also comply with the same parameters of sulfur content as the Premium gasoline (30 ppm average / maximum 80 ppm), a situation that is met in at least one of the three metropolitan areas, but at a very high cost since much of the premium gasoline is imported.

With respect to the rest of the country, the regulation indicates that Magna UBA must be consumed since January 2009, a fact that has been postponed due to the delay in bidding for the PEMEX post-treatment and modernization plants. This situation, of course, makes the Magna gasoline that continues to be consumed in the rest of the country, contain 350 ppm and that the diesel contains 500 ppm instead of 30 ppm that marks the Mexican standard NOM-086, with its respective consequences in the emission of polluting compounds. It is urgent that our country begins to have UBA gasoline and diesel.

Therefore, for the production of a fuel with an ultralow sulfur content, the HDS of 99% of the sulfur compounds present in the hydrocarbon mixture (HCs) is necessary, among which are benzothiophenes and dibenzothiophenes alkyl. replaced.

Several studies, including that of Laredo et al., "Nitrogen compounds characterization in atmospheric gas oil and light cycle oil from a blend of Mexican crudes". Fuel 81, 2002, pgs. 1341-1350, have mainly shown that: • The catalytic reaction of HDS is significantly inhibited by organic nitrogenous compounds, · There is a competitive adsorption between nitrogen and sulfur compounds by the active sites of the catalyst, which causes nitrogenous compounds to poison HDS catalysts, • The amount of inhibition depends on the type and concentration of the organic nitrogenous compounds, and · In direct streams of light fuel feed, the average total nitrogen content is 100 to 300 ppm; while, in heavier currents, such as light cyclic oil, the total nitrogen content is greater than 500 ppm.

Taking into account that nitrogenous compounds are strong inhibitors in the HDS of sulfur compounds, great efforts have been made in the world scientist to develop pre-treatment processes for the selective removal of nitrogen compounds from the diesel and gasoline feed streams. In these currents of HCs are basic nitrogen compounds: aniline, pyridine, acridine and quinoline, and their derivatives with alkyl substituents; and non-basic: pyrrole, indole, carbazole, and their derivatives.

Serban et al., In "Diesel desulfurization to make ULSD - overcoming nitrogen inhibition", UOP LLC, to Honeywell Company, 2008, studied the effect of catalyst poisoning in the HDS process by nitrogenous compounds, demonstrating that even a few traces of 3-ethylcarbazole could have a huge impact on HDS of 4,6-diethyldibenzothiophene because the alkylcarbazoles are highly refractive and could be adsorbed and block the active sites of catalyst.

The use of physical adsorption methods for the selective removal of nitrogen compounds is an attractive proposal, because the adsorption can be carried out at room temperature and atmospheric pressure without the need for the use of hydrogen.

Some of the technologies that have been developed to solve this problem are the use of solid adsorbents such as those used by SK Corporation in South Korea: "Method for manufacturin cleaner fuels", US 6,248,230 B1, granted on June 19, 2001 , where Min et al., provide a process of nitrogen removal that consists of the use of several adsorbents, among which are named: silica, aluminas, ion exchange resins and activated carbon.

Recently, the extraction of nitrogen compounds through the use of Lis has been of great interest to the international scientific community. The Lis have been known for more than 30 years, but their boom in different industrial applications started approximately in the last 10 years. They are applied as solvents and catalysts in alkylation, polymerization and Diels-Alder, in addition to being used in electrochemical processes, but its most interesting use is as solvents for the extraction of gases and different impurities based aromatic and heterocyclic compounds of HCs, among others.

There is a diversity of published works on the subject of extraction of sulfur and nitrogen compounds of HCs, such as: • "lonic liquids on desulfurization of fuel oils", Francisco et al., Fluid Phase Equilibria, 2010, 294, pages: 39-48., And • "Extraction · Ability of Nitrogen-Containing Compounds Involved in the Desulfurization of Fuels by Using Lonic Liquids". Alonso et al., Journal of Chemical & Engineering Data, 2010, Vol. 55, No. 9, pages: 3262-3267., They deal with the desulfurization and denitrogenation of HCs using Lys containing fluorine in their structure.

Several works are dedicated to this application using Lys containing in their anionic part halides and / or salts of metals, for example: • In US patent application 2010/0270211 A1, dated October 28, 2010, Ryszard A. Wolny incorporates the use of LIS and metal ion systems for the removal of nitrogen and sulfur compounds from mixtures of HCs; • In the international patent application WO 2011/026972 A1, published on March 10, 2011, Gerrit Jan Harmsen et al., Implement the use of: Lys type tetrachloroferrate; • In the article "Selective extraction of neutral nitrogen compounds found in diesel feed by 1-butyl-3-methyl-imidazolium chloride", Green Chemistry, 2008, 10, pp .: 524-531, Xie et al., Use Lis with chloride as an anion for the selective removal of nitrogenous compounds of diesel; • In the article "[bmimjAICU lonic Liquid for Deep Desulfurization of Real Fuels", Energy & Fuels, 2008, 22, pp .: 1774-1778, Roland Schmidt, reports the extraction of nitrogenous compounds from diesel using Lys containing aluminum cations in its structure; Y • In the article "Parallel Microwave-Assisted Synthesis of Lonic Liquids and Screening for Denitrogenation of Straight-Run Diesel Feed by Liquid-üquid Extraction", Combinatorial Chemestry & High Throughput Screening, 2012, Vol. 15, No. 5, pp .: 427-432, Cerón et al., Refer to the extraction of nitrogen compounds from HCs, using different Lis, imidazole and pyridine derivatives, where it is important to emphasize that , said Lys contain in their anionic part halides and / or metal salts.

On the other hand, it is important to point out that halides free of halides and metals lately attract scientific attention because this class of Lis are more friendly to the environment, as Almeida et al., Illustrate in "Thermophysical Properties of Five Acetate" -Based íonic Liquids ", Journal of Chemical & Engineering Data, 2012, 57, 3005-3013.

In this regard, there are two large groups of halide-free Lis: 1) . Lis protics, type Bronsted acids, and 2) . Lis aprotic.

The synthesis of protic Lys, type Bronsted acids, is well known and consists of an acid neutralization reaction with an organic base, usually an amine, as reported in: • "An efficient protocol for the synthesis of 2-amino-4,6-diphenylpyridine-3-carbonitrile using ionic liquid ethylammonium nitrate", Sarda et al., Mol Divers, 2009, 13, pp .: 545-549; Y · "Thermophysical properties of binary mixtures of { Ionic liquid 2-hydroxy ethylammonium acetate + (water, methanol, or ethanol).", Alvarez et al., J. Chem. Thermodynamics, 2011, 43, pp .: 997-1010).

The synthesis of aprotic Lys, free of halides, is carried out in two reaction stages, based on the alkylation method (Stage 1) by a methylsulfate or halogenoalkane, as reported in: "Synthesis and Optical Properties of 1-Alkyl-3-Methylimidazolium Lauryl Sulfate lonic Liquids ", Obliosca et al., J Fluoresc, 2007, 17, pp .: 613-618, and in the anion exchange (Stage 2), as reported in: "Amino-Functionalized Lonic Liquid as A Nucleophilic Scavenger in Solution Phase Combinatorial Synthesis", Song et al, Journal of Combinatorial Chemestry, 2005, Vol. 7, No. 4, pp .: 561-566.

Because the alkylation method (Step 1) by a halogenalkane can cause difficulty in ion exchange in Step 2 by providing the Lis of low purity, the most suitable alkylation method for the synthesis of the Lis is with the use of dimethylcarbonate as a methylating agent, as reported in: "Kinetic Study of the Reaction of Dimethyl Carbonate with Tríalkylamines", Weisshaar et al., International Journal of Chemical Kinetics, 2010, 42, pp .: 221-225, and "Synthesis and Characterization of Lauryl Trimethyl Ammonium Suriactants with New Counteranion Types, "Xu et al., Journal of Surfactants and Detergents, Oct 2009, 12, 4, p. 351-354; according to the following synthesis scheme: Synthesis diagram of halogen free halides with the use of dimethylcarbonate. where: N-R ^ Ra = Tri-alkylamine or a heterocyclic cation or quaternary ammonium base.

(CH30) 2CO = Dimethylcarbonate = N-methyl-trialkylammonium methylcarbonate HA = carboxylic acid or any acid with greater pK of carbonic acid = Ionic liquid obtained with carboxylate base anion.

The Japanese researchers Osamu Yagi and Shumpei Shimuzu in the article "Synthesis of Puré Treatmethylammonium Hydroxide Solution Free from Chone Ion by the Electrolysis of Its Hydrogen Carbonate", Chemistry Letters, 1993, pgs. 2041-2044, describe the use of dimethylcarbonate (DMC) as an amine methylating agent. The method described in said article makes it possible to obtain the s with methylcarbonate type anion, derived from a very weak acid, which is very easy to exchange for any desirable anion derived from carboxylic acid with pKa minor carbonic acid, at very mild conditions. The DMC exhibits a versatile and tunable chemical reactivity that depends on the experimental environments. Under reaction conditions at high temperatures the DMC acts mainly as a methylating agent, while at a reaction temperature equal to or lower than 90 ° C the DMC acts mainly as a methoxycarbonylating agent.

In the works: • "Extractive Desulfurization and Denitrogenation of Fuels Using Lonic Liquids", Ind.

Eng. Chem. Res., 2004, Vol. 43 No. 2, pages: 614-622; Y • "Extractive Desulfurization of Fuel 0/7 Using Alkydazole and Its Mixture with Dialkylphosphate Lonic Liquids", Ind. Eng. Chem. Res., 2007, Vol. 46, No. 15, pp .: 5108-5112, The properties of the Lys were studied to extract sulfur and nitrogen compounds.

In the meantime, in the works: · "Deep oxidative desulfurization with task-specific ionic liquids: An experimental and computational study", Gui et al., Journal of Molecular Catalysis A: Chemical, 2010, 331, pp .: 64-70; • "Deep removal of sulfur from real diesel by catalytic oxidation with halogen-free ionic liquid", Liu et al., Korean J. Chem. Eng., 2012, Vol. 29, No. 1, pp .: 49-53; and · "Oxidation of dibenzothiophene catalyzed by Na2W04 in a haloge-free ionic liquid", Liu et al., Reac Kinet Mech Cat, 2011, 104, pp .: 111-123; The desulfurization of diesel was studied through an oxidation process using Lis with the carboxylic group in the cationic part and sulfuric or phosphoric acids as the anionic part.

In US Patent Application 2005/0010076 A1, published on January 13, 2005, Wasserscheid et al., Make use of LIS to remove polar impurities and heteroatomic compounds from oil currents by requesting protection of practically all possible cations and anions. which can form an L, but giving poor examples with the Lys widely known with aluminum chloride type anions and methylsulfates, without giving any example of LI with carboxylic anions such as acetate or benzoate, although these are included in said patent application .

The works: · "Extraction of Thiophene or Pyridine from n-Heptane Using Lonic Liquids, Gasoline and Diesel Desulfurization", Kedra-Królik et al., Industrial & Engineering Chemistry Research, 2011, 50, pp .: 2296-2306; Y • "Removal of Organic Sulfur from Hydrocarbon Resources Using Lonic Liquids", Mochizuki and Sugawara, Energy & Fuels Vol. 22, No. 5, 2008, pages: 3303-3307; and the Patent Application: _ t • US 2010/0051509 A1, by Martínez Palou et al., Published on March 4, 2010, relates to the desulphurisation of gasolines and diesel with halogen and metal-free lys, where the lys have anions such as thiocyanate, methylsulfate and acetate.

However, there are several works about halides free of halides and metals for application as catalysts in chemical reactions, among others: • "Synthesis of coumarins via Pechmann reaction catalyzed by 3-methyl-1-sulfonic acid imidazolium hydrogen sulfate as an efficient, halogen-free and reusable acidic ionic liquid", Nader Ghaffari Khaligh, Catalysis Science & Technology, 2012, 2, pp .: 1633-1636; • "Camphor lonic Liquid: Correlation between Stereoselectivity and Cation-Anion Interaction", Nobuoka et al., J. Org. Chem. 2005, Vol. 70, No. 24, pages: 10106-10108; • "Lonic Liquids Promoted the C-Acylation of Acetates in Solvent-free Conditions", Martins et al., Catal Lett, 2009, 130, pp .: 93-99; • "Synthesis of dimethyl carbonate catalyzed by carboxylic functionalized imidazolium salt via transesterification reaction", Wang et al., Catalysis Science & Technology, 2012, 2, pp .: 600-605; • "Preparation, characterization and use of 1, 3-disulfonic acid imidazolium hydrogen sulfate as an efficient, halogen-free and reusable ionic liquid catalyst for the trimethylsilyl protection of hydroxyl groups and deprotection of the obtained trimethylsilanes", Shirini et al., Journal of Molecular Catalysis A: Chemical, 2012, 365, pp .: 15-23; • "Natural Amino Acid-Based Lonic Liquids as Efficient Catalysts for the Synthesis of Cyclic Carbonates from CO2 and Epoxides under Solvent-Free Conditions", Wu et al., Letters in Organic Chemistry, 2010, Vol. 7, No. 1, p. .: 73-78; Y • "Symmetrical and unsymmetrical Bmnsted acidic ionic liquids for the effective conversion of fructose to 5-hydroxymethyl furfural", D. A. Kotadia and S. S. Soni, Catalysis Science & Technology, 2013, 3, pp .: 469-474.

: The halide-free ortho-borate derivatives have the potential to be applied in metal ion extraction processes or as steel / aluminum lubricants, as referred to in: • "Halogen-free chelated orthoborate ionic liquids and organic ionic plastic crystals", Shah et al., Journal of Materials Chemistry, 2012, 22, 6928-6938; Y • "Novel halogen-free chelated orthoborate-phosphonium ionic liquids: synthesis and tribophysical properties", Shah et al., Phys. Chem. Chem. Phys., 2011, 13, pp .: 12865-12873.

In addition, there are studies on the use of halogen-free Lys as additives for the breakdown of azeotropes in extractive distillation, such as, for example, Shen et al., "Effect of the lonic Liquid Triethylmethylammonium Dimethylphosphate on the Vapor Pressure of Water, Methanol, Ethanol, and Their Binary Mixtures," Journal of Chemical & Engineering Data, 2011, 56, pp .: 1933-1940, or as additives in the processes of protein purification by crystallization, such as that of Hekmat et al., "Advanced protein crystallization using water-soluble ionic liquids as crystallization additives ", Biotechnol Lett, 2007, 29, pp .: 1703-1711.

None of the mentioned references suggests and much less claims ionic liquids (Lis) base methylcarbonate or carboxylates (not limited only to acetates and benzoates), process of obtaining and using; in the removal of organic nitrogen or nitrogen compounds: aliphatic and aromatic, contaminants of hydrocarbon mixtures (HCs); through a process of selective extraction LI-HCs, at room temperature and atmospheric pressure, where the Lis are immiscible with the HCs.

It is therefore an object of the present invention to provide novel methylcarbonate based bases or carboxylates, aliphatic or aromatic carboxylic acid derivatives.

Another object of the present invention is to provide a synthesis process of the new Lis having the general formula C + A ", where: C + is a heterocyclic or quaternary ammonium organic cation, and A "is a methylcarbonate base anion or carboxylates derived from aliphatic or aromatic carboxylic acids.

A further object of the present invention is to provide the main use of the new Lis to remove organic nitrogen or nitrogen compounds: aliphatic and aromatic, contaminants of mixtures of HCs, where mixtures of HCs to denitrogenar are preferably petroleum-based fuels: gasoline, diesel, light cyclic oil and turbosine, as well as other streams of HCs obtained in the oil refining processes.

BRIEF DESCRIPTION OF THE DIAMETERS OF THE NONDION Figure No. 1. Figure No. 1 shows the graphical results of the extraction of nitrogenous compounds from a mixture of primary light gas oil (LPG) hydrocarbons with N-methyl-triethylammonium butanoate (Ll 2), using a system of continuous flow. ' DETAILED DESCRIPTION OF THE INVENTION The present invention relates to new ionic liquids (Lys) base methylcarbonate or carboxylates, derivatives of aliphatic or aromatic carboxylic acids, production process and use in the removal of organic nitrogen or nitrogen compounds: aliphatic and aromatic, contaminants of hydrocarbon mixtures (HCs); by means of a liquid-liquid selective extraction process (LI-HCs), at room temperature and atmospheric pressure, where the Lys are immiscible with the HCs, due to the higher affinity of the organic nitrogenous compounds through the medium of L to the medium of HCs in which they are present. Said process is carried out through a stirring extraction of the two phases, followed by a separation stage, or in a continuous flow system, where the nitrogenous compounds pass to the phase formed by the Ll and as a result the total content of Nitrogen is considerably reduced in the HC phase.

Mixtures of HCs to be denitrogenated by the present invention are preferably petroleum-derived fuels: gasoline, diesel, light cyclic oil and turbosine; as well as other streams of HCs obtained in the oil refining processes.

The new Lises of the present invention have the general formula C + A ", where: C + is a heterocyclic organic cation or quaternary ammonium base.

The heterocyclic organic cation is preferably imidazolium, pyridinium or isoquinolinium base.

The imidazolium-based heterocyclic organic cation preferably consists of benzyl, aromatic, cycloalkyl, alkenyl or aliphatic substituents of 1 to 10 carbon atoms, more preferably 2 to 8 carbon atoms.

The pyridinium-based heterocyclic organic cation preferably consists of benzyl, cycloalkyl, aromatic or aliphatic chain substituents of 1 to 10 carbon atoms.

The isoquinolinium-based heterocyclic organic cation is preferably constituted by benzyl, alkenyl, cycloalkyl, aromatic or aliphatic chain substituents of 1 to 10 carbon atoms.

The quaternary ammonium base cation preferably consists of benzyl, alkenyl, cycloalkyl, aromatic or aliphatic chain substituents of 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.

The heterocyclic organic cation or quaternary ammonium base is more preferably of the types: tetraalkyl ammonium, alkyl pyridinium and alkyl imidazolium.

A 'is a base anion methylcarbonate or carboxylates, preferably constituted by alkyl, cycloalkyl, benzyl, alkenyl, aromatic or alkyl functionalized alkyl chain substituents, of 1 to 18 carbon atoms, such as butanoate, hexanoate and octanoate.

The general structure of the cations and anions, which constitute the new Lys of the present invention, are shown in Table No. 1.

Table No. 1. General structure of cations and anions, that constitute the new Lis SYNTHESIS PROCESS OF THE NEW Lis The new Lises of the present invention were prepared according to the following scheme of synthesis of two reaction stages: I) N-R3 + (CH30) 2CO + N-R4 / CH3OCOO- II) + N-R4 / CH3OCOO '+ R-COOH -? + N-R4 / R-COO where: N-R3 = Tri-alkylamine and the R groups of N-R3 = Benzilic, aromatic, cycloalkyl, alkenyl and / or aliphatic chains, of 1 to 20 carbon atoms, more preferably of 1 to 10 carbon atoms (CH30) 2CO = Dimethylcarbonate + N-R4 / CH3OCOO "= N-methyl-trialkylammonium methylcarbonate R-COOH = carboxylic acid or any acid with greater pK of carbonic acid + N-R4 / R-COO ~ = alkyl-, aryl-carboxylate of N-methyl-trialkylammonium and the R group of R-COO = alkyl, cycloalkyl, benzyl, alkenyl, aromatic or alkyl functionalized chain, of 1 to 18 carbon atoms.

I. In reaction step I, a heterocyclic organic compound or quaternary ammonium base (Example: N-R3 = Tri-alkylamine) is reacted with a methylcarbonate base compound or carboxylates (Example (CH3O) 2CO = Dimethylcarbonate), agitation, for a time of 3 to 12 h,: a; a temperature of 110 to 180 ° C and pressure of 0 to 300 psi, to finally wash the Ll formed with heptane and dried under vacuum; Y In reaction stage II, the ionic liquid (Ll) formed in reaction stage I (Example + NR / CH 3 OCOO "= N-methyl-trialkylammonium methylcarbonate), with carboxylic acid (R-COOH) or any other acid is treated. with greater pK of carbonic acid, by means of agitation for 15 to 30 min, at temperature environment, to obtain the corresponding ionic liquid (Ll), which is dried in vacuum for its subsequent spectroscopic characterization; The ionic liquids (Lis) obtained, methylcarbonate base or carboxylates, aliphatic or aromatic carboxylic acid derivatives, have the general formula: C + A where: C + is a heterocyclic organic cation or quaternary ammonium base, and A "is a methylcarbonate base anion or carboxylates.

With all the modalities previously indicated.

USE OF THE NEW Lis IN THE DENITROGENATION OF HCs The use of the new Lys, methylcarbonate base or carboxylates, for the removal of organic nitrogen or nitrogen compounds: aliphatic and aromatic, contaminants of mixtures of HCs, comprises the following stages: a) Mixed. To put in contact the Ll, base methylcarbonate or carboxylates, with the mixture of HCs that contain as organic pollutants or impurities nitrogen or nitrogen, in a ratio between the mass of HCs from 1: 1,000,000 to 999: 1, to initiate the interaction between the Ll and the HCs; b) Liquid-liquid selective extraction (LI-HCs). Shake the mixture obtained: in step a), for 1 to 120 min., At room temperature and atmospheric pressure, so that the L can remove or extract organic compounds of nitrogen or nitrogen, contaminants or impurities of the HCs, until the separation of the phase of the mixture of Ll of the phase of HCs; Y c) Separation. The new phases of Ll and HCs obtained in stage b); they physically separate from each other. Now the new phase of Ll contains the organic compounds of nitrogen or nitrogen, contaminants or impurities of Ibs HCs, and the new phase of HCs contains a reduced amount or no amount detectable of said nitrogen or nitrogen organic compounds, contaminants or impurities of the HCs.

The ratio between the mass of Ll to HCs is preferably 1: 100; the variation of this relationship depends on the identity and physical properties of the HCs to be processed and on the LI used, as well as the concentration, nature and solubility of the organic compounds of nitrogen or nitrogen, contaminants or impurities of the HCs.

The liquid-liquid selective extraction time (LI-HCs), preferably is from 1 to 30 min.

When the present invention is used in one or more extraction stages or in a continuous flow system, the nitrogen compounds pass into the phase formed by the L1 and as a result the total nitrogen content is considerably reduced in the HC phase.

EXAMPLES Some practical examples are described below to have a better understanding of the present invention, without this limiting its scope.

SYNTHESIS OF NEW Lis Examples No. 1 to 4 Stage I: Synthesis of N-methyl-trialkylammonium methylcarbonate. 100 mmol of trialkylamine and 200 mmol of dimethylcarbonate are mixed in a batch reactor. The mixture is kept under stirring for a time of 5 to 10 h, at a temperature of 120 to 170 ° C and pressure of 30 to 250 psi. After the reaction the product is obtained as a viscous liquid, viscous semi-solid or yellow solid, which is washed with heptane and dried under vacuum.

Stage II: Synthesis of N-methyl-trialkylammonium carboxylate.

In a glass reactor, provided with a stirring system, 10 mmol of N-methyl-trialkylammonium methylcarbonate, obtained in Step I, are dissolved in 10 ml of methanol. Then 10 mmol of the corresponding acid are dosed, the mixture is stirred for 20 min at room temperature, obtaining a viscous amber colored liquid. The methanol is evaporated and the lll obtained is dried in vacuo.

The spectroscopic characterization is performed through Nuclear Magnetic Resonance of 1H and 13C, using deuterated chloroform and deuterated dimethylsulfoxide as solvents, the displacements are indicated in parts per million (d) with respect to the tetramethylsilane signal (TMS) as internal standard.

The spectroscopic characteristics of the new Lis synthesized, as well as the obtained yields are shown below: Ll 1. N-methyl-triethylammonium methylcarbonate Ll 1 was obtained as a yellow solid, with a yield of 92%. IR (film): 2942, 1661, 1436, 1274, 1065, 862, 821 cm "1. 1 H NMR (300 MHz, CDCl 3), d? (ppm): 1.38 (t, 9H, J = 7.40 Hz), 3.23 (s, 3H), 3.47 (s, 3H), 3.56 (ct, 6H, .7 = 7.44 Hz). 13 C NMR (75 MHz, CDCl 3), o c (ppm): 7.95 (3 C), 46.90, 50.58, 55.60 (3 C), 159.6 (COO).

Ll 2. N-methyl-triethylammonium butanoate The Ll 2 was obtained in the form of an amber liquid, with a yield of 89%.

IR (film): 2959, 2872, 1564, 1457, 1389, 1 192, 1010, 784 cm "1. 1 H NMR (300 MHz, CDCl 3), d? (ppm): 0.91 (t, 3H, J = 7.42 Hz), 1.36 (t, 9H, J = 7.14 Hz), 1.61 (sxt, 2H, J = 7.29 Hz), 2.14 (t, 2H, J = 7.56 Hz) ), 3.15 (s, 3H), 3.51 (ct, 6H, J = 7.24 Hz). 13 C NMR (75 MHz, CDCl 3), 6 C (ppm): 7.91 (3 C), 14.45, 20.12, 40.65, 46.88, 55.64 (3 C), 179.00 (COO).

Ll 3. N-methyl-triethylammonium hexanoate The Ll 3 was obtained in the form of amber colored viscous liquid, with a yield of 90%.

IR (film): 2955, 2856, 1562, 1458, 1390, 1 192, 1010 cm "1. 1 H NMR (300 MHz, CDCl 3), d? (ppm): 0.85 (t, 3H, J = 3.43 Hz), 1.28-1.38 (m, 13H), 1.58 (m, 2H), 2.14 (t, 2H, J = 7.64 Hz), 3.16 (s, 3H) , 3.53 (ct, 6H, J = 7.24 Hz). 13 C NMR (75 MHz, CDCl 3), d 0 (ppm): 7.91 (3C), 14.16, 22.69, 26.83, 32.27, 38.99, 46.86, 55.60 (3C), 179.34 (COO).

Ll 4. N-methyl-triethylammonium octanoate The Ll 4 was obtained in the form of amber colored viscous liquid, with a yield of 91%.

IR (film): 2924, 2853, 1569, 1457, 1383, 1 192, 101 1, 81 1 crn "1. 1 H NMR (300 MHz, CDCl 3), d? (ppm): 0.86 (t, 3H, J = 3.43 Hz), 1.27-1.38 (m, 17H), 1. 58 (m, 2H), 2.16 (t, 2H, J = 7.8 Hz), 3.17 (s, 3H), 3.52 (ct, 6H, J = 7.14 Hz). 13 C NMR (75 MHz, CDCl 3), o c (ppm): 7.92 (3 C), 14.13, 22.57, 27.16, 29.37, 30.02, 31. 92, 39.05, 46.83, 55.60 (3C), 179.48 (COO).

USE OF NEW Lis Example No. 5 Denitrogenation of Model Mixtures (MM), in a single stage of extraction with Ll These examples were made with a model mixture (MM) prepared by dissolving nitrogen compounds such as quinoline, aniline, indole and carbazole at 739, 335, 586 and 1, 797 ppm respectively, and benzothiophene as the sulfur compound at a concentration of 42,000. ppm in a toluene / n-hexadecane solvent system (1: 1), with a total nitrogen concentration of 350 ppm.

The MM was treated with each of the new Lis obtained by means of Examples Nos. 1 to 4: Ll 1. N-methyl-triethylammonium methylcarbonate Ll 2. N-methyl-triethylammonium butanoate Ll 3. N-methyl-triethylammonium hexanoate Ll 4. N-methyl-triethylammonium octanoate Using a ratio of 1 to 20 of LI: MM, a single liquid-liquid selective extraction (LI-HCs) was carried out, during 0.5 hours, at room temperature and atmospheric pressure. After separation in two phases, the content of nitrogen compounds was determined by gas chromatography. The chemical structure of some of the LIS employees is shown in Table No. 2, as well as the comparative results of the LIS employees.

Table No. 2. Removal of nitrogen compounds in MM, in a single extraction stage with Ll, using a ratio of 1: 20 of LI: MM.

The results of Table No. 2 show that the Lis with anion base methylcarbonate and free carboxylates of haiogenides and metals lower the nitrogen content of the original model sample containing 350 ppm of total nitrogen, ratifying that its use in the removal is feasible of organic nitrogenous compounds of mixtures of HCs, such as: gasoline, diesel, light cyclic oil, turbosine and diesel, and. other streams of HCs obtained in the oil refining processes.

Likewise, it is important to note that the sulfur contents in the samples of model HCs reported in Table No. 2, after the extraction process with the LIS, practically do not vary, which confirms the affinity of the LIS towards the compounds nitrogen.

Finally, Table No. 2 shows that Lys 2 to 4 have greater selectivity for indole, carbazole and aniline nitrogenous compounds, practically extracting 100% of indole from HCs.

Example No. 6 Denitrogenation of Model Mixtures (MM), in several stages of extraction with Ll The process is the same as that of Example No. 5; however, the L1 that had been used once for denitrogenation of the MM again was used with a fresh portion of MM in a second, third, and optionally more extraction stages, with a ratio of 1 to 40 of LI: MM . The results are shown in Table No. 3.

Table No. 3. Removal of nitrogen compounds in MM, in several stages of extraction with Ll 2, using a ratio of 1: 40 of LI: MM.

The results of Table No. 3 demonstrate the efficiency of the extraction process of the present invention and the capacity of the Lys to remove the nitrogenous compounds in several stages, without any purification of the L employed.

In Table No. 3 it is shown that the Ll 2 presents a constant removal of the nitrogenous compounds that in its maximum point is of 67% and that is decreasing little by little as it is adding new load, in each stage of extraction the efficiency it decays around 5%, which allows to consider the halides free of halides and metals as good candidates to operate in continuous flow extraction processes.

Example No. 7 Denitrogenation of hydrocarbon mixtures type LPG, in continuous flow extraction systems with LV.

This example was carried out with a mixture of primary light gas oil (LPG) hydrocarbons, which had a total nitrogen concentration of 273 ppm. The test was carried out continuously in a glass column with a volume of 10 ml, packed with inert material (Pyrex glass) at a mesh size of 35/40 and containing 6 g of Ll 2. They were passed about 1 L of LPG with a nitrogen content of 273 ppm, at a flow rate of 0.17 ml / min at room temperature and atmospheric pressure. The percentage of total nitrogen extraction against the accumulated volume of the load in me for each g of Ll 2 is shown in Figure No. 1.

In Figure No. 1 it is observed that the Ll 2 presents a constant removal of the nitrogenous compounds, its maximum point was 51% and it was decreasing little by little as it was adding new load. This material has a great capacity for removal, reaching up to 20% removal of nitrogen compounds after having treated 130 ml / g of Ll 2 in a continuous flow extraction system.

Claims (1)

1. NOVELTY OF THE INVENTION What is claimed is: Ionic liquids based on methylcarbonate or carboxylates, derivatives of aliphatic or aromatic carboxylic acids, of the general formula: C + A where: C + is a heterocyclic organic cation or quaternary ammonium base, and A 'is a methylcarbonate base anion or carboxylates. Ionic liquids based on methylcarbonate or carboxylates, according to clause 1, wherein the heterocyclic organic cation is preferably of imidazolium, pyridinium or isoquinolinium base. Ionic liquids based on methylcarbonate or carboxylates, according to clauses 1 and 2, wherein the imidazolium-based heterocyclic organic cation preferably consists of benzyl, aromatic, cycloalkyl, alkenyl or aliphatic substituents of 1 to 10 carbon atoms, more preferably from 2 to 8 carbon atoms. Ionic liquids based on methylcarbonate or carboxylates, according to clauses 1 and 2, wherein the pyridinium-based heterocyclic organic cation is preferably constituted by benzyl, cycloalkyl, aromatic or aliphatic chain substituents of 1 to 10 carbon atoms. Ionic liquids based on methylcarbonate or carboxylates, according to clauses 1 and 2, wherein the isoquinolinium-based heterocyclic organic cation is preferably constituted by chain substituents. benzyl, alkenyl, cycloalkyl, aromatic or aliphatic, from 1 to 10 carbon atoms. Ionic liquids based on methylcarbonate or carboxylates, according to clause 1, wherein the quaternary ammonium base cation is preferably constituted by benzyl, alkenyl, cycloalkyl, aromatic or aliphatic substituents of 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. Ionic liquids based on methylcarbonate or carboxylates, according to clauses 1 to 6, wherein the heterocyclic organic cation or quaternary ammonium base is more preferably of the types: tetraalkyl ammonium, alkyl pyridinium and alkyl imidazolium. Ionic liquids based on methylcarbonate or carboxylates, according to clauses 1 to 7, wherein the base anion carboxylates, preferably consists of alkyl, cycloalkyl, benzyl, alkenyl, aromatic or alkyl functionalized alkyl substituents, of 1 to 18 carbon atoms, such as: butanoate, hexanoate, octanoate and salicylate. A process for obtaining the methylcarbonate or carboxylate base ionic liquids of clause 1, comprising two reaction stages: I) In reaction stage I, a heterocyclic organic compound or quaternary ammonium base compound is reacted with a methylcarbonate base compound or carboxylates, by stirring, for a time of 3 to 12 h, at a temperature of 1 10 to 180 ° C and pressure from 0 to 300 psi, to finally wash the ionic liquid (Ll) formed with heptane and dry it under vacuum; Y II) In reaction stage II, the ionic liquid (Ll) formed in reaction stage I, with carboxylic acid or any acid with greater pK of carbonic acid, is treated by stirring for 15 to 30 min, at room temperature, to obtain the corresponding ionic liquid (Ll), which is dried in vacuum for its subsequent spectroscopic characterization; The ionic liquids (Lis) obtained, methylcarbonate base or carboxylates, aliphatic or aromatic carboxylic acid derivatives, have the general formula: C + A where: C * is a heterocyclic organic cation or quaternary ammonium base, and A "is a methylcarbonate base anion or carboxylates. 10. A process for the preparation of ionic liquids base methylcarbonate or carboxylates, according to clause 9, wherein the heterocyclic organic cation is preferably imidazolium, pyridinium or isoquinolinium base. 11. A process for the preparation of ionic liquids base methylcarbonate or carboxylates, according to clause 9, wherein the imidazolium-based heterocyclic organic cation is preferably constituted by benzyl, aromatic, cycloalkyl, alkenyl or aliphatic substituents of 1 to 10 atoms of carbon, more preferably from 2 to 8 carbon atoms. 12. A process for the preparation of ionic liquids base methylcarbonate or carboxylates, according to clause 9, wherein the pyridinium based heterocyclic organic cation preferably consists of benzyl, cycloalkyl, aromatic or aliphatic substituents of 1 to 10 carbon atoms . 13. A process for the preparation of ionic liquids base methylcarbonate or carboxylates, according to clause 9, wherein the heterocyclic organic cation of isoquinolinium base is preferably constituted by benzyl, alkenyl, cycloalkyl, aromatic or aliphatic substituents of 1 to 10 carbon atoms. 14. A process for the preparation of ionic liquids based on methylcarbonate or carboxylates, according to clause 9, wherein the quaternary ammonium base cation is preferably constituted by benzyl, alkenyl, cycloalkyl, aromatic or aliphatic substituents of 1 to 20 carbon atoms , more preferably from 1 to 10 carbon atoms. 15. A process for the preparation of ionic liquids base methylcarbonate or carboxylates, according to clauses 9 to 14, wherein the base anion carboxylates, preferably consists of alkyl, cycloalkyl, benzyl, alkenyl, aromatic or alkyl functionalized alkyl substituents, to 18 carbon atoms, such as butanoate, hexanoate, octanoate and salicylate. 16. Use of ionic liquids base methylcarbonate or carboxylates, derivatives of aliphatic or aromatic carboxylic acids, of the general formula: C + A where: C * is a heterocyclic organic cation or quaternary ammonium base, and A 'is a methylcarbonate base anion or carboxylates, in the removal of organic nitrogen or nitrogen compounds: aliphatic and aromatic, contaminants of hydrocarbon mixtures (HCs), through a liquid-liquid selective extraction process (LI-HCs), at room temperature and atmospheric pressure. 17. Use of ionic liquids base methylcarbonate or carboxylates, according to clause 16, wherein the heterocyclic organic cation is preferably based on imidazolip, pyridinium or isoquinolinium. 18. Use of ionic liquids based on methylcarbonate or carboxylates, in accordance with clauses 16 and 17, wherein the imidazolium-based heterocyclic organic cation preferably consists of benzyl, aromatic, cycloalkyl, alkenyl or aliphatic substituents of 1 to 10 carbon atoms , more preferably from 2 to 8 carbon atoms. 19. Use of ionic liquids based on methylcarbonate or carboxylates, according to clauses 16 and 17, wherein the pyridinium-based heterocyclic organic cation is preferably constituted by benzyl, cycloalkyl, aromatic or aliphatic chain substituents of 1 to 10 carbon atoms. 20. Use of ionic liquids based on methylcarbonate or carboxylates, according to clauses 16 and 17, wherein the isoquinolinium-based heterocyclic organic cation preferably consists of benzyl, alkenyl, cycloalkyl, aromatic or aliphatic substituents of 1 to 10 carbon atoms . 21. Use of ionic liquids base methylcarbonate or carboxylates, according to clause 16, wherein the quaternary ammonium base cation preferably consists of benzyl, alkenyl, cycloalkyl, aromatic or aliphatic substituents of 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. 22. Use of ionic liquids base methylcarbonate or carboxylates, according to clauses 16 to 21, wherein the heterocyclic organic cation or quaternary ammonium base is more preferably of the types: tetraalkyl ammonium, alkyl pyridinium and alkyl imidazolium. 23. Use of ionic liquids base methylcarbonate or carboxylates, according to clauses 16 to 22, wherein the base anion carboxylates, preferably consists of alkyl, cycloalkyl, benzyl, alkenyl, aromatic or alkyl functionalized substituents, from 1 to 18 carbon atoms. carbon, such as: butanoate, hexanoate, octanoate and salicylate. 24. Use of ionic liquids based on methylcarbonate or carboxylates, in accordance with clauses 16 to 23, where mixtures of hydrocarbons (HCs) to denitrogenate are preferably petroleum derived fuels. 25. Use of ionic liquids based on methylcarbonate or carboxylates, in accordance with clause 24, where the fuels derived from petroleum to denitrogenate are preferably: gasoline, diesel, light cyclic oil and turbosine, as well as other streams of HCs obtained in the refining processes of the oil. 26. Use of ionic liquids based on methylcarbonate or carboxylates, in accordance with clauses 16 to 25, where the liquid-liquid selective extraction process (LI-HCs), at room temperature and atmospheric pressure, comprises the following steps:. . a) Mixed. To put in contact the Ll, methylcarbonate base or carboxylates, with the mixture of HCs that contain as organic pollutants or impurities nitrogen or nitrogen compounds, in a ratio between the mass of Ll to HCs of 1: 1, 000,000 to 999: 1; b) Liquid-liquid selective extraction (LI-HCs). Stir the mixture obtained in step a), for 1 to 120 min., At room temperature and atmospheric pressure, until the separation of the phase of the mixture of Ll from the HC phase; Y c) Separation. The new phases of Ll and HCs obtained in stage b) are physically separated from each other. 27. Use of ionic liquids base methylcarbonate or carboxylates, in accordance with clause 26, where the ratio between the mass of Ll to HCs is preferably 1: 100. 28. Use of ionic liquids based on methylcarbonate or carboxylates, in accordance with clause 26, where the liquid-liquid selective extraction time: LI-HCs, preferably is from 1 to 30 min. 29. Use of ionic liquids base methylcarbonate or carboxylates, in accordance with clauses 26 to 28, where the process of selective extraction liquid - liquid (LI-HCs), is carried out in one or more stages of extraction and extraction systems of continuous flow.