PORTABLE SYSTEM FOR DETERMINING MONOETHYLENE GLYCOL

Abstract

The present invention discloses a portable system comprised of an electrochemical cell for batch injection analysis (BIA) coupled to a copper oxide electrode for the selective determination and quantification of monoethylene glycol (MEG) from different petrochemical samples with application in the environment laboratory and in field analyses, aiming at the quality control of these samples by portable methodology and in a short analysis time.

Claims

1. PORTABLE SYSTEM FOR DETERMINING MONOETHYLENE GLYCOL, characterized in that it comprises an electrochemical cell by batch injection (BIA) (1), where said cell comprises a working electrode (2) of copper oxide, an auxiliary electrode (3) of stainless steel and an Ag/AgCl.sub.sat reference electrode (4), coupled to an electronic micropipette (5) and a stirring system (6).

2. PORTABLE SYSTEM FOR DETERMINING MONOETHYLENE GLYCOL, according to claim 1, characterized in that the batch injection electrochemical (BIA) cell (1) is manufactured from polymeric material.

3. PORTABLE SYSTEM FOR DETERMINING MONOETHYLENE GLYCOL, according to claim 1, characterized in that the flow rate of the electronic micropipette (5) is in the range of 4 to 28 μL/s of sample.

4. PORTABLE SYSTEM FOR DETERMINING MONOETHYLENE GLYCOL, according to claim 3, characterized in that the flow rate of the electronic micropipette (5) is 4 μL/s of sample.

5. PORTABLE SYSTEM FOR DETERMINING MONOETHYLENE GLYCOL, according to claim 1, characterized in that the copper oxide working electrode (2) is at the voltage in the range of 0.35 to 0.55 V.

6. PORTABLE SYSTEM FOR DETERMINING MONOETHYLENE GLYCOL, according to claim 5, characterized in that the copper oxide working electrode (2) is at the voltage of 0.45 V.

7. PORTABLE SYSTEM FOR DETERMINING MONOETHYLENE GLYCOL, according to claim 1, characterized in that the electrodes (2, 3 and 4) are immersed in a support electrolyte under agitation (6).

8. PORTABLE SYSTEM FOR DETERMINING MONOETHYLENE GLYCOL, according to claim 7, characterized in that the basic support electrolyte is 0.5 mol/L NaOH.

9. PORTABLE SYSTEM FOR DETERMINING MONOETHYLENE GLYCOL, according to claim 1, characterized in that the stirring system (6) is made by a magnetic stirrer.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0022] The present invention will be described in more detail below, with reference to the attached figures which, in a schematic and non-limiting way, represent examples of the configuration thereof. In the drawings, there are:

[0023] FIG. 1 illustrating the elements of BIA cell (1) of present invention comprising a working electrode (2), an auxiliary electrode (3) and a reference electrode (4), and having an electronic micropipette coupling (5) and a stirring system (6);

[0024] FIG. 2 illustrating the cyclic voltammograms of monoethylene glycol samples diluted in 0.5 mol/L NaOH and scanning from −800 to 800 V at a speed of 20 mV/s;

[0025] FIG. 3 illustrating the optimization of micropipette instrumental parameters for the use in BIA analyses;

[0026] FIG. 4 illustrating the injection in duplicate of 25 mmol/L monoethylene glycol with and without a stirring system, with an applied voltage of 0.55 V and a speed of 20 mV/s;

[0027] FIG. 5 illustrating BIA-amperograms of real sample subjected to different stirring times (0.5-5 minutes) for MEG extraction, oxidation voltage of 0.55 V and speed of 20 mV/s;

[0028] FIG. 6 illustrating BIA-amperograms of a real sample extracted in different proportions of solvent extractor (v/v), with an oxidation potential of 0.55 V and a speed of 20 mV/s;

[0029] FIG. 7 illustrating the detection potentials for analysis in BIA cell of the present invention aiming at eliminating signals of diethylene glycol (DEG), triethylene glycol (TEG) and ethanol (EtOH) as possible interferents in the quantification of monoethylene glycol (MEG).

DETAILED DESCRIPTION OF THE INVENTION

[0030] The portable system according to the present invention, and illustrated in FIG. 1, comprises an electrochemical cell for batch injection (BIA) analysis made of polymeric material. The BIA cell (1) is comprised of a working electrode (2) of copper oxide, an auxiliary electrode (3) of stainless steel and a reference electrode (4) of Ag/AgCl.sub.sat.

[0031] The invention can be applied in different matrices having MEG, requiring only to extract the analyte of interest in the basic medium, preferably 0.5 mol/L NaOH, which makes up the support electrolyte. In addition, the method allows for analyses with a MEG detection limit of 0.23 mol/L.

[0032] The BIA cell (1) uses a copper oxide working electrode (2) that presents an analytical response with a voltage range of 0.35 and 0.55 V. The voltage of 0.45 V is preferably used to discriminate the monoethylene glycol of the main alcohols present in the condensate samples, thus reducing interferents.

[0033] The portable system uses a potentiostat (not shown in FIG. 1) coupled for amperometric analysis by batch injection. In this type of analysis, the electrodes are immersed in a basic solution, preferably 0.5 mol/L NaOH (supporting electrolyte), under agitation, in which volumes in the range of 2 μL to 20 μL (preferably 15 μL) of sample are injected directly under the working electrode (2). The sample is introduced by means of an electronic micropipette (5) with flow rate and injected volume controlled, and the agitation is done by a magnetic stirrer (6).

[0034] The analytical response is given by peak whose intensity is directly proportional to the concentration of MEG in the sample. Regarding batch analyses, it is possible to use the cell for the whole day of analysis performing successive tests with less than 100 mL of waste generation.

[0035] The electro-oxidation of the species was carried out in a uStat400 potentiostat/galvanostat (DropSens S.L., Oviedo, Spain) and monitored by a software DropView®. Injections were performed with the aid of an electronic micropipette (5) (Multipette® stream—Eppendorf) with 100 μL Combitip®.

[0036] The BIA cell (1) used, but not limited to these types of electrodes, is comprised of a working electrode (2) of copper oxide, an auxiliary electrode (3) of stainless steel and, as a reference electrode (4) of Ag/AgCl.sub.sat. The distance from Combitip® to the working electrode (2) was approximately 2 mm. The cell structure was printed by a Prusa Movitech® 3D printer using polylactic acid (PLA) as substrate. The cell shows, preferably, cylindrical dimensions of approximately 5.0 cm in height and diameter, and its configurations are designed with the help of software AutoCAD®, and can be manufactured with different materials and with other dimensions.

EXAMPLES

[0037] For this study, tests were carried out as follows, which represent embodiment examples of present invention.

Example 1: Monoethylene Glycol Oxidation Test

[0038] The electro-oxidation process was studied, using the cyclic voltammetry technique, with the aim at evaluating the BIA cell (1) and observing at which voltages the MEG would be oxidized.

[0039] The tests were performed with 0.5 mol/L NaOH and it can be seen in the voltammograms obtained in FIG. 2 that, from 0.35 V to 0.8 V, the oxidation of monoethylene glycol occurs. From 0.6 V onwards, there are also signs of oxygen evolution, as observed in the electrolyte analysis.

[0040] Thus, aiming at analyses with greater sensitivity and without harming the stability of the electrode, 0.5 mol/L NaOH was preferentially chosen as the electrolyte for the next steps.

Example 2: Optimization Test of Electronic Micropipette Parameters

[0041] In batch injection analyses, factors such as sample volume and flow velocity interfere with the current obtained. In general, this current obtained is directly proportional to the injected sample volume. Tests were carried out to optimize these parameters with a standard solution of 25 mmol/L MEG in 0.5 mol/L NaOH. As shown in FIG. 3, it is noted that volumes below 5.0 μL result in relatively low currents, increasing the detection limit. Regarding larger volumes, there was no significant difference between the volumes of 10, 15 and 20 μL, which resulted in a greater current signal. In this way, all these volumes can be used, being recommended the volume of 15 μL as it shows the smallest standard deviation among the replicates.

[0042] Among the five injection rates analyzed, a response was obtained for values between 4.0 and 28.0 μL/s. It was noticed that the current obtained is inversely proportional to the flow. It is recommended, preferably, a flow of 4.0 μL/s.

Example 3: Stirring System Test

[0043] Analyzes in BIA cells (1) can be performed with or without a stirring system (6), and these parameters are evaluated according to analytical frequency and repeatability.

[0044] FIG. 4 shows the current intensity obtained from the injection of the same monoethylene glycol solution in duplicate with and without agitation. The current intensity did not show great variation, which demonstrates the feasibility of the analysis in both modes. On the other hand, the experiment with agitation showed better repeatability with faster analyses. The analysis time without agitation was approximately 100 s, whereas with agitation it was 30 s. Based on these data, it is recommended to carry out the analyzes using a magnetic stirrer.

Example 4: Analysis of Real Sample by Pattern Addition Method

[0045] Analyses with a real kerosene sample were performed by the standard addition method. Initially, MEG extraction conditions were optimized. As the sample must be diluted in the supporting electrolyte (preferably 0.5 mol/L NaOH) used in the BIA cell (1), this electrolyte was used as an extracting solvent, since the literature reports that monoethylene glycol is soluble in aqueous solutions. For such, the sample was added in NaOH 0.5 mol/L in the proportion 50% (v/v) causing the system to be stirred.

[0046] Afterwards, the sample was left to rest for 1 minute, in order to separate the phases. The aqueous phase, comprised of the electrolyte with the MEG that was expected to be extracted, was collected and analyzed. The stirring time for extraction was standardized according to the signal obtained in the electrochemical tests, as shown in FIG. 5. Signals of MEG were observed for values from 0.5 minutes of agitation. After 2 minutes of shaking there was no significant change in signal. Thus, we chose to preferentially use the value of 3 minutes due to its better precision between replicates (SD=3).

Example 5: Extractor Solvent Volume Test

[0047] It is known that the greater the volume of extracting solvent, the greater the amount of analyte to be extracted, but the aqueous phase will be more diluted. Knowing this, the test was carried out in different proportions of extracting solvent in order to find the condition in which the aqueous phase would show a greater analytical response. As noted in FIG. 6, the best results were obtained for an extraction performed with 50% (v/v) of extracting solvent.

Example 6: Interferent Studies

[0048] Since the copper electrode is not selective, tests were carried out to observe the oxidation profile of possible interferents in petroleum condensate samples, seeking to improve the accuracy of the method.

[0049] It was observed in which voltages the oxidation of other diols similar to MEG (diethylene glycol-DEG and triethylene glycol-TEG) and of ethanol—EtOH occurs. As shown in FIG. 7, it is noted that monoethylene glycol is the first of the compounds to start its oxidation, and up to approximately 0.45 V only it shows changes in current. Later, it was noted the beginning of oxidation of the other glycols, DEG and TEG, but with much lower intensity than MEG. At the voltage used for the previous analyses, 0.55 V, it is observed that even EtOH shows an oxidation signal. Thus, it is concluded that depending on the source of the real sample, in addition to the use of the standard addition method, the use of oxidation voltages close to 0.45 V is of priority to eliminate any sign of possible interferents.

[0050] Given the examples, it can be shown that the BIA cell (1) of the present invention presents a robust, practical and portable instrumentation, providing satisfactory results, with better sensitivity compared to traditional amperometric methods.

[0051] It can still be stated that portability, together with the low demand for sample volume and minimal waste generation, are strong advantages of using the cell for batch injection analysis (BIA). In addition to these advantages, the results obtained, in terms of analytical performance and selectivity in relation to other diols, and to ethanol demonstrate that present system is superior to traditional amperometric methods

[0052] It should be noted that, although the present invention has been described with respect to the attached drawings, modifications and adaptations can be made by those skilled in the art, depending on the specific situation, but provided that it is within the inventive scope defined herein.