Ionic liquids, methylcarbonate- or carboxylates-based, obtaining process and use thereof

Abstract

Methylcarbonate-based ionic liquids (LIs) or carboxylates, derived from aliphatic or aromatic carboxylic acids are provided for the extraction of nitrogen compounds from hydrocarbon mixture (HCs) by liquid-liquid selective extraction, at room temperature and atmospheric pressure, where the LIs are immiscible with the HCs. This process is performed through an extraction by stifling two phases, followed by separation, or in a continuous flow system where the nitrogenous compounds are transferred to the phase formed by the LI and the total nitrogen content is substantially reduced in the HCS phase. The ionic liquids have the general formula 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.

1 . Methylcarbonate-based ionic liquids or carboxylates, derived from aliphatic or aromatic carboxylic acids, of general formula:
   C+A−
   Where:
 C+ is a heterocyclic organic cation or quaternary ammonium-based, and 
 A− is a methylcarbonate- or carboxylates-based anion. 
   
     
     
         2 . Methylcarbonate- or carboxylates-based ionic liquids, according to  claim 1 , wherein the heterocyclic organic cation is preferably imidazolium, pyridinium or isoquinolinium-based. 
     
     
         3 . Methylcarbonate- or carboxylates-based ionic liquids, according to  claim 1 , wherein the imidazolium-based heterocyclic organic cation preferably is comprised by substituents of benzyl, aromatic, cycloalkyl, alkenyl or aliphatic chains, from 1 to 10 carbon atoms, more preferably from 2 to 8 carbon atoms. 
     
     
         4 . Methylcarbonate- or carboxylates-based ionic liquids, according to  claim 1 , wherein the pyridinium-based heterocyclic organic cation preferably is comprised by substituents of benzyl, cycloalkyl, aromatic or aliphatic chains, from 1 to 10 carbon atoms. 
     
     
         5 . Methylcarbonate- or carboxylates-based ionic liquids, according to  claim 1 , wherein the isoquinolin-based heterocyclic organic cation preferably is comprised by substituents of benzyl, alkenyl, cycloalkyl, aromatic or aliphatic chains, from 1 to 10 carbon atoms. 
     
     
         6 . Methylcarbonate- or carboxylates-based ionic liquids, according to  claim 1 , where the quaternary ammonium-based cation preferably is comprised by substituents of benzyl, alkenyl, cycloalkyl, aromatic or aliphatic chains, from 1 to 20 carbon atoms, more preferably from 1 to 10 carbon atoms. 
     
     
         7 . Methylcarbonate- or carboxylates-based ionic liquids, according to  claim 1 , wherein the quaternary ammonium-based heterocyclic organic cation or more preferably is of two types: tetralkylammonium, and alkyl pyridinium and alkyl imidazolium. 
     
     
         8 . Methylcarbonate- or carboxylates-based ionic liquids, according to  claim 1 , wherein the carboxylates-based anion, preferably is comprised by substituents of alkyl, cycloalkyl, benzyl, alkenyl, alkyl or aromatic functionalized chains, from 1 to 18 carbon atoms, such as: butanoate, hexanoate, octanoate and salicylate. 
     
     
         9 . A process for obtaining the Methylcarbonate- or carboxylates-based ionic liquids of  claim 1 , which comprises two stages of reaction:
 I) In the reaction stage I, a heterocyclic organic compound or a quaternary ammonium-based compound is reacted with methylcarbonate- or carboxylates-based, by stifling, for a period of 3 to 12 h, at a temperature of 110 to 180° C. and a pressure of 0 to 300 psi, to finally wash the ionic liquid (LI) formed with heptane and dry them in the vacuum; and   II) In the reaction stage II, ionic liquid (LI) is treated which was formed in the reaction stage I, with carboxylic acid or any acid with higher pK of carbonic acid, by stifling for 15 to 30 min at room temperature, in order to obtain the corresponding ionic liquid (LI), which is dried to vacuum for the subsequent spectroscopic characterization;
 Ionic liquids (LIs) obtained, methylcarbonate- or carboxylates-based, derived from aliphatic or aromatic carboxylic acids, have the general formula:
   C+A−
 
 
   Where:
 C+ is a heterocyclic organic cation or quaternary ammonium-based, and 
 A− is a methylcarbonate- or carboxylates-based anion. 
   
     
     
         10 . A process for obtaining Methylcarbonate- or carboxylates-based ionic liquids, according to  claim 9 , wherein the heterocyclic organic cation is preferably imidazolium, pyridinium or isoquinolinium-based. 
     
     
         11 . The process for obtaining Methylcarbonate- or carboxylates-based ionic liquids, according to  claim 9 , wherein the imidazolium-based heterocyclic organic cation preferably is comprised by substituents of benzyl, aromatic, cycloalkyl, alkenyl or aliphatic chains, from 1 to 10 carbon atoms, more preferably from 2 to 8 carbon atoms. 
     
     
         12 . The process for obtaining Methylcarbonate- or carboxylates-based ionic liquids, according to  claim 9 , wherein the pyridinium-based heterocyclic organic cation preferably is comprised by substituents of benzyl, cycloalkyl, aromatic or aliphatic chains, from 1 to 10 carbon atoms. 
     
     
         13 . The process for obtaining Methylcarbonate- or carboxylates-based ionic liquids, according to  claim 9 , wherein the organic cation of heterocyclic isoquinolinium-based preferably is comprised by substituents of benzyl, alkenyl, cycloalkyl, aromatic or aliphatic chains, from 1 to 10 carbon atoms. 
     
     
         14 . The process for obtaining Methylcarbonate- or carboxylates-based ionic liquids, according to  claim 9 , where the quaternary ammonium-based cation preferably is comprised by substituents of benzyl, alkenyl, cycloalkyl, aromatic or aliphatic chains, from 1 to 20 carbon atoms, more preferably from 1 to 10 carbon atoms. 
     
     
         15 . The process for obtaining Methylcarbonate- or carboxylates-based ionic liquids, according to  claim 9 , where the carboxylates based-anion, preferably is comprised by substituents of alkyl, cycloalkyl, benzyl, alkenyl, alkyl or aromatic functionalized chains, from 1 to 18 carbon atoms, such as: butanoate, hexanoate, octanoate and salicylate. 
     
     
         16 . The use of methylcarbonate-based ionic liquids or carboxylates, derived from aliphatic or aromatic carboxylic acids, of general formula:
   C+A−
   Where:
 C+ is a heterocyclic organic cation or quaternary ammonium-based, and 
 A− is a methylcarbonate- or carboxylates-based anion, 
 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. 
   
     
     
         17 . The use of Methylcarbonate- or carboxylates-based ionic liquids, according to  claim 16 , wherein the heterocyclic organic cation is preferably imidazolium, pyridinium or isoquinolinium-based. 
     
     
         18 . The use of Methylcarbonate- or carboxylates-based ionic liquids, according to  claim 16 , wherein the imidazolium-based heterocyclic organic cation preferably is comprised by substituents of benzyl, aromatic, cycloalkyl, alkenyl or aliphatic chains, from 1 to 10 carbon atoms, more preferably from 2 to 8 carbon atoms. 
     
     
         19 . The use of Methylcarbonate- or carboxylates-based ionic liquids, according to  claim 16 , wherein the pyridinium-based heterocyclic organic cation preferably is comprised by substituents of benzyl, cycloalkyl, aromatic or aliphatic chains, from 1 to 10 carbon atoms. 
     
     
         20 . The use of Methylcarbonate- or carboxylates-based ionic liquids, according to  claim 16 , wherein the isoquinolin-based heterocyclic organic cation preferably is comprised by substituents of benzyl, alkenyl, cycloalkyl, aromatic or aliphatic chains, from 1 to 10 carbon atoms. 
     
     
         21 . The use of Methylcarbonate- or carboxylates-based ionic liquids, according to  claim 16 , wherein the quaternary ammonium-based cation preferably is comprised by substituents of benzyl, alkenyl, cycloalkyl, aromatic or aliphatic chains, from 1 to 20 carbon atoms, more preferably from 1 to 10 carbon atoms. 
     
     
         22 . The use of Methylcarbonate- or carboxylates-based ionic liquids, according to  claim 16 , wherein the organic cation heterocyclic quaternary ammonium-based or more preferably is of two types: tetralkylammonium, and alkyl pyridinium and alkyl imidazolium. 
     
     
         23 . The use of Methylcarbonate- or carboxylates-based ionic liquids, according to  claim 16 , where the base anion carboxylates, preferably is comprised by substituents of chains alkyl, cycloalkyl, benzyl, alkenyl, alkyl or aromatic functionalized, from 1 to 18 carbon atoms, such as: butanoate, hexanoate, octanoate and salicylate. 
     
     
         24 . The use of Methylcarbonate- or carboxylates-based ionic liquids, according to  claim 16 , where hydrocarbon mixture (HCs) to denitrogenate preferably are oil-based fuels. 
     
     
         25 . The use of Methylcarbonate- or carboxylates-based ionic liquids, according to  claim 24 , wherein oil-based fuels to denitrogenate preferably are: gasoline, diesel, oil and lightweight cyclical turbosine, as well as other HCs streams obtained in the processes of oil refining. 
     
     
         26 . The use of Methylcarbonate- or carboxylates-based ionic liquids, according to  claim 16 , where the process of liquid-liquid selective extraction (LI-HCs), at room temperature and atmospheric pressure involves the following steps:
 a) Mixing. Put the LI in contact, methylcarbonate- or carboxylates-based, with the mixture of HCs that contain impurities or pollutants as nitrogen organic or nitrogenous compounds, in a ratio between the mass of LI to HCs of 1:1,000,000 to 999:1, to start the interaction between the LI 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 LI remove or extracts nitrogen organic or nitrogenous compounds, pollutants or impurities of the HCs, until the separation of the phase of the LI mixture of the HCS phase; and   c) Separation. The new phases of LI and HCs obtained in phase b), are separated physically between thereof. Now the new phase of LI contains nitrogen organic or nitrogenous compounds, pollutants or impurities of the HCs, the new HCS phase. contains a reduced amount or any amount detectable of said nitrogen organic or nitrogenous compounds, pollutants or impurities of the HCs.   
     
     
         27 . The use of Methylcarbonate- or carboxylates-based ionic liquids, according to  claim 26 , where the ratio between the mass of LI to HCs preferably is 1:100. 
     
     
         28 . The use of Methylcarbonate- or carboxylates-based ionic liquids, according to  claim 26 , where the time of liquid-liquid selective extraction: LI-HCs, preferably is from 1 to 30 min. 
     
     
         29 . The use of Methylcarbonate- or carboxylates-based ionic liquids, according to  claim 26 , where the process of liquid-liquid selective extraction (LI-HCs), is carried out in one or more stages of extraction and extraction systems in continuous flow.