A method and device for regulating the air demand of extractive Merox units. The present invention relates to a method for tracking the conversion of mercaptans into disulfides, in which a hydrocarbon load containing mercaptans is brought into contact with a basic aqueous solvent to produce a mercaptan-depleted hydrocarbon fraction and a mercaptan-enriched aqueous phase, said mercaptan-enriched aqueous phase being separated and brought into contact with a gas containing oxygen to produce insoluble disulfides and a regenerated basic aqueous solvent.
Liquefied petroleum gas (LPG) derived from crude oil fractionation, petroleum fractions or cracking methods generating it, is generally charged with light organo-sulfur compounds. Among the organo-sulfur compounds identified in this LPG, there are mercaptans such as methylmercaptan and ethylmercaptan, as well as hydrogen sulfide (H2S). The mercaptans are compounds with the formula R—SH where R is a linear, ramified or cyclic alkyl group. The hydrogen sulfide (H2S) is not therefore considered as a mercaptan in the present application. The mercaptans likely to be present in an LPG generally exhibit a C1-C6 carbonated chain, although longer carbonated chains may also be present.
In addition to direct commercial use in motor vehicles with controlled ignition, LPG is a raw material useful in producing ethyl tert-butyl ether (ETBE) or methyl tert-butyl ether (MTBE), which are used in formulating commercial gasolines. The LPG used to produce ETBE/MTBE must have a sulfur content less than 15 ppm. This constraint makes it necessary to optimize the operation of the LPG “extractive Merox” units.
The “extractive Merox” units extract the mercaptans from the LPG and convert them into disulfides. The method can be summarized as follows: an LPG charged with sulfur compounds is washed by an alkaline aqueous solution, usually sodium hydroxide, in order to produce, on the one hand, a sulfur compound-depleted LPG and, on the other hand, an alkaline aqueous solution comprising mercaptans in salified form. The latter is separated and brought together with oxygen to transform the mercaptans into disulfides and water. The disulfide-forming reaction is usually catalyzed by cobalt phthalocyanine, according to a method developed by UOP. The disulfides obtained are not soluble in water and are separated by decanting. The separated alkaline aqueous solution is recycled. The cobalt phthalocyanine used remains in the alkaline aqueous solution.
The extractive Merox unit is controlled by varying the quantity of air injected into the catalytic zone so as to obtain a total conversion into disulfides with no excess of air. Operation with an excess of air results in an input of oxygen in the mercaptan extractor. The oxygen reacts with the mercaptans to form disulfides which will not be extracted by the alkaline aqueous solution and will remain in the LPG.
In the regenerated soda, the mercaptan content, in the form of sodium thiolates, should be between 30 and 100 ppm. CH3CH2SNa, CH3SNa and C6H5SNa are nonlimiting examples of sodium thiolates. CH3CH2SH, CH3SH and C6H5SH are nonlimiting examples of mercaptans.
Typically, the extractive Merox unit is controlled, with respect to the oxygen demand, by means of a visual test called “shake test”. This test consists in half-filling a transparent glass bottle with the soda solution after regeneration (the top part of the bottle containing air), in plugging the bottle and in shaking it until there is a color change. The color changes from blue to green when the cobalt catalyst changes degree of oxidation. If the color change occurs in less than 30 seconds, there may be an excess of air. The assessment of this color can vary depending on the operator performing the operation.
When the soda solution has a dark color, for example black (presence of impurities), the shake test is showing its limits. Similarly, a rapid change of color does not necessarily mean an excess of air but can also signify a low proportion of mercaptans or a highly active and/or highly concentrated catalyst. Moreover, a degraded or diluted soda solution will not be effective enough for extracting the mercaptans from the LPG and will also falsify the results.
There are therefore needs to obtain a reliable test for determining the oxygen demands of the alkaline aqueous solution, for example a 15% soda solution.
To this end, and according to a first aspect of the invention, the applicant has found a method for tracking the conversion of mercaptans into disulfides, in which a hydrocarbon load containing mercaptans is brought into contact with a basic aqueous solvent to produce a mercaptan-depleted hydrocarbon fraction and a mercaptan-enriched aqueous phase, said mercaptan-enriched aqueous phase being separated and brought into contact with a gas containing oxygen to produce insoluble disulfides and a regenerated basic aqueous solvent, characterized in that the progress of the insoluble disulfide-producing reaction is monitored by measuring redox potential.
The applicant has found, surprisingly, that despite the many parameters likely to interfere with the measurement of the redox potential, the latter was able to be used to control the reaction, for example by monitoring the input of gas containing oxygen (O2). The parameters likely to interfere are, for example, the temperature, the pH, the concentration of the redox couples in solution and their solubilities, a corrosive action of the measured solution and a poisoning of the measurement electrode by the sulfur compounds. Many redox couples are in fact likely to be present, originating for example from the catalyst used to catalyze the mercaptan-to-disulfide oxidation reaction, for example the phthalocyanine-complexed cobalt, but also originating from the different species of mercaptans present in the hydrocarbon load. The redox potential measurements performed in a corrosive environment can be falsified as a result of corrosion of the electrode. The basic aqueous solution used may in fact be a very basic 15% solution of soda. Similarly, it is known that some electrodes (for example the Ag/AgCl electrodes) are poisoned by H2S which leads to their deterioration. Such poisoning is also likely to occur in the presence of other sulfur compounds, such as the mercaptans.
The electrodes that can be used are, for example, silver electrodes (Ag/AgCl), preferably comprising a protection, for example of polymer type.
The hydrocarbon load used preferably has an H2S content less than or equal to 50 ppm by weight.
The hydrocarbon load may be a liquefied petroleum gas, for example derived from crude oil fractionation, petroleum fractions or cracking methods. The H2S content of the load may, for example, be reduced to a content less than or equal to 50 ppm by weight by at least one wash using an appropriate alkaline aqueous solution.
The redox potential measurement is performed preferably on the regenerated basic aqueous solvent.
The input of gas containing oxygen is regulated according to the measured redox potential.
The basic aqueous solvent is advantageously soda at 10 to 20% by weight, for example 15% by weight. The input of gas containing oxygen is increased or reduced when the redox potential is, respectively, less than −550 mV or greater than −500 mV relative to a hydrogen normal electrode (ENH).
According to a second aspect, the invention relates to a unit for converting mercaptans into disulfides, comprising a first chamber in which a hydrocarbon load containing mercaptans is brought into contact with a basic aqueous solvent to produce a mercaptan-depleted hydrocarbon fraction and a mercaptan-enriched aqueous phase, said mercaptan-enriched aqueous phase being separated and brought into contact with an oxidant in a second chamber to produce insoluble disulfides and a regenerated basic aqueous solvent, the unit for converting mercaptans into disulfides also comprising means for measuring redox potential.
The unit for converting mercaptans into disulfides is, for example, of “extractive Merox” type.
The first chamber, configured to receive and bring into contact a hydrocarbon load containing mercaptans and a basic aqueous solvent to produce a mercaptan-depleted hydrocarbon fraction and a mercaptan-enriched aqueous phase, is, for example, a mercaptan extractor, notably intended for an “extractive Merox” unit.
The second chamber, configured to receive and bring into contact said separated mercaptan-enriched aqueous phase and an oxidant to produce insoluble disulfides and a regenerated basic aqueous solvent, is, for example, an oxidation reactor, notably intended for an “extractive Merox” unit.
The unit preferably comprises a third separation chamber in which the insoluble disulfides and the regenerated basic aqueous solvent are separated.
According to a preferred embodiment, the unit comprises a first duct for returning the regenerated basic aqueous solvent from the third chamber to the first chamber.
Advantageously, the means for measuring redox potential of the unit are arranged on the third chamber and/or on the first duct.
The means for measuring redox potential arranged on the first duct and/or on the third chamber comprise a probe for measuring redox potential coupled to a reading appliance.
The measuring means are advantageously connected to the first duct using a bypass duct.
The bypass duct may also comprise an isolating valve, a water intake for cleaning the measuring probe and the chamber supporting it, and a drain valve.
According to a third aspect, the invention relates to a kit for measuring the redox potential of a corrosive solution comprising (i) a duct feeding corrosive solution, (ii) a duct feeding water, (iii) a tank, (iv) a probe for measuring redox potential, (v) a drain, and optionally a reading appliance coupled to the probe.
Such a kit forms a device for sampling and measuring the redox potential of a corrosive solution, which can be used to implement the method according to the invention.
The kit may comprise means for isolating the different sections consisting of (i) the duct feeding corrosive solution and/or (ii) the duct feeding water and/or (ii) the tank, and/or (iii) the drain.
In particular, the kit comprises a tank equipped with a potential-measuring probe, a duct intended to feed the tank with corrosive solution, a duct intended to feed the tank with water, a drain for the tank, at least one means for isolating the duct feeding corrosive solution and at least one means for isolating the duct feeding water. These isolation means are, for example, valves.
The probe for measuring redox potential, optionally coupled to a reading appliance, optionally comprises means for coupling to means for regulating the feed of gas containing oxygen such as those present in a mercaptan conversion unit according to the second aspect of the invention.
According to a fourth aspect, the invention relates to the use of the kit according to its third aspect, in a refining installation, or even a refining installation comprising a sampling and measuring kit or device according to the invention.
The use of the kit may comprise the steps of:
This use may optionally comprise a step for controlling gas feed regulating means for a chamber from which the corrosive solution to be measured originates, for example an oxidation reactor, in order for the measured redox potential to lie within a predetermined range of values.
The invention is now described with reference to the attached
In
The curve which represents the variation of the concentration of mercaptans of the soda solution at 15% by weight as a function of the redox potential exhibits a first inflection in the region of −500 mV and a second inflection in the region of −550 mV. This curve is representative of the potential at which the mercaptans (in the form of anions, represented symbolically by RS−) are oxidized into disulfides (symbolically represented by RSSR).
In operation, the setpoint of concentration of mercaptans in the regenerated soda derived from an extractive Merox is usually between 30 and 100 ppm (zone A). Thus, in the present case, a redox potential of between −500 mV and −550 mV is maintained. When the measured redox potential is less than −550 mV (zone B), there is an oxidation defect which can be eliminated by increasing the air flow rate into the installation. When the measured redox potential is greater than −500 mV (zone C), there is an excess of air which can be corrected by reducing the air flow rate into the installation.
In
When the quantity of oxygen (O2) added to the oxidation reactor 13 is insufficient, the reaction oxidizing the mercaptans into disulfides is incomplete, so that there remain mercaptans in the three-phase mixture of oxygen-depleted air, insoluble disulfides and regenerated soda 15 leaving the oxidation reactor 13. These mercaptans collect in the mercaptan-depleted soda 8 reinjected at the head of the mercaptan extractor 7 and in the LPG collected at the head of the extractor 7.
When the quantity of oxygen added to the oxidation reactor 13 is too great, the oxygen is not fully consumed and collects in the three-phase mixture of oxygen-depleted air, insoluble disulfides and regenerated soda 15 leaving the oxidation reactor 13, then in the mercaptan-depleted soda 8 reinjected at the head of the mercaptan extractor 7. The presence of oxygen (O2) dissolved in the mercaptan-depleted soda 8 leads to the formation of disulfides in the mercaptan extractor 7, which will collect in the LPG collected at the head of the extractor 7.
Thus, an excess of air or a lack of air, in other words an excess of O2 or a lack of O2, results in an LPG containing mercaptans or disulfides and not meeting the specifics required for ETBE/MTBE production.
A device for measuring redox potential according to the invention can be incorporated into the conventional LPG desulfurizing installation described above. Such a device makes it possible to control the feed of air 12 in order for the oxidation reaction within the oxidation reactor 13 to be complete.
In
A device conforming to
The use of this technique has made it possible to raise the conformity rate of the LPG used to manufacture ETBE from 20% to 80%, over an annual average, the remaining nonconformities being attributed to other operational issues, notably linked to the presence of residual H2S.
A device conforming to
Three eight-hour aging tests in the soda at 15% were carried out. After each test, a check on the electrode by means of a reference fluid (Hanna HI7021 at 240 mV) is performed in order to observe whether an abnormal aging of the electrode has occurred. The latter did not register any drift, which shows that the integrity of the electrode was not affected.
Number | Date | Country | Kind |
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10 59662 | Nov 2010 | FR | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/FR11/52719 | 11/22/2011 | WO | 00 | 6/25/2013 |