FR2829771A1 - Process for the desulfuration and/or denitrogenation of a hydrocarbon mixture, useful in the purification of fuels, involves oxidation and solvent extraction of the oxidized compounds - Google Patents

Abstract

A process of desulfuration and/or denitrogenation of a hydrocarbon mixture comprises an oxidation stage followed by an extraction of the oxidized products with a solvent containing adiponitrile and/or 1,2-propylene carbonate.

Description

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Process for desulphurisation and / or denitrogenation of a hydrocarbon mixture
The present invention relates to a process for desulfurizing and / or denitrogenating a mixture of hydrocarbons, such as petroleum fractions such as fuels, containing sulfur compounds and / or nitrogen compounds. The process comprises an oxidation step for oxidizing the sulfur compounds and / or the nitrogen compounds, which is followed by a step of removing the oxidized compounds by extraction using an extraction solvent.

 On the one hand, for environmental reasons, specifications on the sulfur content of fuels are becoming more and more severe. On the other hand, for reasons related to certain catalytic refining operations, the presence of basic nitrogen compounds must be limited. It is known that this type of compounds can poison the catalysts used in these operations (hydrodesulfurization and catalytic cracking).

 It is known to reduce the sulfur and / or nitrogen content of fuels by a process comprising a step of oxidizing the sulfur compounds and / or nitrogen compounds followed by a step of removing these oxidized compounds. It is also known to remove these oxidized compounds by various means, for example by physical treatment such as extraction with a solvent immiscible with the fuel, or adsorption on a solid, or by distillation or by cold precipitation. It may also be a chemical treatment such as pyrolysis or alkaline hydrolysis.

 One of the known solvents, which gives satisfactory results in the solvent extractions, is dimethylsulfoxide, which is used, for example, in US Pat. No. 6,160,193. This solvent has in fact a good ability to extract oxidized sulfur compounds and allows at the same time to limit the losses of petroleum hydrocarbons by non-selective extraction of these hydrocarbons. In other words, this solvent has a good selectivity for extracting the oxidized sulfur compounds from a petroleum fraction and thus reducing the sulfur concentration in the petroleum fraction. However, it has the major disadvantage of introducing sulfur into the oil cut, a substance that is desired to eliminate the oil cut. Its use in a process of high desulfurization (to reach a final concentration of sulfur for example lower

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 at 10 ppm) then requires a step of total elimination of the residual solvent contained in the oil cut. In addition, dimethylsulfoxide has a high toxicity.

 The present invention aims to avoid the aforementioned drawbacks while keeping the good performance of dimethylsulfoxide, and thus to provide a process which contains an extraction step using an extraction solvent which simultaneously has the following properties: a good power extraction of oxidized sulfur compounds and / or oxidized nitrogen compounds; a good selectivity in order to limit the hydrocarbon losses that would be extracted by the solvent; very little contamination of the hydrocarbon mixture by the extraction solvent; the absence of sulfur in the solvent, when the process aims to desulphurize, and the absence of basic nitrogen in the solvent, when the process aims to de-nitrogenize; good compatibility, particularly in terms of density, with a wide range of different hydrocarbon mixtures; good resistance to oxidation; preferably, a lower toxicity than that of dimethylsulfoxide.

 The invention therefore relates to a process for the desulphurisation and / or denitrogenation of a mixture of hydrocarbons containing sulfur-containing compounds and / or nitrogen compounds, comprising an oxidation step using an oxidizing agent in order to oxidize the sulfur-containing compounds and / or the nitrogenous compounds, followed by a step of extracting the oxidized sulfur compounds and / or the oxidized nitrogen compounds by means of an extraction solvent, in which the extraction solvent contains adiponitrile and / or 1,2-propylene carbonate.

The extraction step of the process according to the invention consists of:
1) contacting the extraction solvent and the hydrocarbon mixture resulting from the oxidation step, by any appropriate means, under conditions ensuring that a separation into two or more distinct and immiscible liquid phases takes place occurs. In the case where two phases are present, there is a first phase consisting essentially of the mixture of hydrocarbons depleted in oxidized sulfur compounds and / or oxidized nitrogen compounds, and another phase consisting essentially of the extraction solvent and oxidized sulfur compounds and or oxidized nitrogen compounds.

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2) a separation of the phases from the previous step (1) by any appropriate means so as to recover the phase consisting essentially of the hydrocarbon mixture depleted of oxidized sulfur compounds and / or oxidized nitrogen compounds.

 The extraction step according to the method of the invention can be carried out in continuous or discontinuous mode. Continuous mode is preferred. Examples of devices usable for extraction are described in the Encyclopedia Ullmann's Encyclopedia of Industrial Chemistry, Fifth Edition, 1988, Volume B-3, pages 6-14 to 6-21.

 In the extraction step of the process according to the invention carried out in batch mode, the extraction solvent is used in an amount such that the ratio of the volumes of the hydrocarbon mixture resulting from the oxidation step and the extraction solvent is generally greater than or equal to 0.1, in particular greater than or equal to 1, preferably greater than or equal to 4. The volume ratio is usually less than or equal to 100, more especially less than or equal to 50 , ratios lower or equal to 20 being the most common.

 In the extraction step of the process according to the invention carried out in continuous mode, the extraction solvent is used in an amount such that the ratio of the flow rates of the hydrocarbon mixture resulting from the oxidation step and the extraction solvent entering the extraction device is generally greater than or equal to 0.1, in particular greater than or equal to 1, preferably greater than or equal to 4. The ratio of flow rates is usually less than or equal to 100, more especially less than or equal to 50, the ratios less than or equal to 20 being the most common.

 In the extraction step of the process according to the invention carried out in batch mode, it may be advantageous to carry out several successive extractions using the same extraction solvent.

In the process according to the invention, the extraction solvent contains from 0 to
100% by weight of adiponitrile and 0 to 100% by weight of 1,2propylene carbonate, these two concentrations can not be simultaneously zero. The extraction solvent can therefore consist of: adiponitrile alone. This variant gives good results.

 - 1,2-propylene carbonate alone. This variant is preferred from the point of view of density, toxicity and oxidation resistance.

 a mixture of adiponitrile and 1,2-propylene carbonate. In this case, the ratio of the masses of adiponitrile and 1,2-propylene carbonate is

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 generally greater than or equal to 0.01, in particular greater than or equal to 0.1.

 The mass ratio is usually less than or equal to 100, more preferably less than or equal to 10. a mixture of adiponitrile and one or more other extraction solvents.

In this case, the ratio of the masses of adiponitrile and other solvent (s) is generally greater than or equal to 0.01, in particular greater than or equal to
0.1. The mass ratio is usually less than or equal to 1000, more preferably less than or equal to 10.

a mixture of 1,2-propylene carbonate and one or more other extraction solvents. In this case, the ratio of the masses of 1,2-propylene carbonate and other solvent (s) is generally greater than or equal to
0, 01, in particular greater than or equal to 0.1. The mass ratio is usually less than or equal to 1000, more especially less than or equal to
10.

a mixture of adiponitrile, 1,2-propylene carbonate and one or more other extraction solvents.

 The use of a single extraction solvent is preferred.

 It is not excluded that the extraction solvent contains impurities in an amount of up to 5% by weight, contents up to 3% by weight being common.

 The other extraction solvent that can be used in the process according to the invention is preferably immiscible with the hydrocarbon mixture, miscible with adiponitrile and / or 1,2-propylene carbonate in the proportions used, and such that the mixture with adiponitrile and / or 1,2-propylene carbonate has a density greater than or equal to 0.95 or less than or equal to 0.80. Examples of this other extraction solvent are water and ethylene carbonate. Water is preferred.

 The water content in the extraction solvent is generally greater than or equal to 0.1% by weight and preferably greater than or equal to 0.25% by weight.

Values greater than or equal to 0.5% by weight are preferred. The water content in the extraction solvent is generally less than or equal to 5% by weight and preferably less than or equal to 4% by weight. Values less than or equal to 3% by weight are preferred.

 By "hydrocarbon mixture" is meant any product containing predominantly hydrocarbons such as paraffins, olefins, naphthenic compounds and aromatic compounds. It can be oil

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 crude or a petroleum derivative obtained by any known refining treatment. The hydrocarbon mixture can be chosen from petroleum fractions that are used in the composition of any type of fuel and fuel. These include kerosene, car fuels such as gasoline or diesel, and domestic fuels such as heating oil.

 Particularly interesting results are obtained when the hydrocarbon mixture which is subjected to the oxidation stage contains hydrocarbons with 10 or more carbon atoms (in particular from 10 to 50 carbon atoms, and most often from 10 to 40 carbon atoms) in an amount of greater than 50% by weight, in particular greater than or equal to 60% by weight.

 The process according to the invention is particularly effective when the hydrocarbon mixture contains aromatic hydrocarbons in an amount of less than or equal to 80% by weight, in particular less than or equal to 50% by weight, the values less than or equal to 40% by weight giving good results. Values less than or equal to 30% by weight are particularly preferred. By "aromatic hydrocarbons" is meant all compounds measured by the method described in IP 391 (1995).

 By "sulfur compounds" is meant all pure compounds and all compounds present in the hydrocarbon mixture, which contain sulfur.

It is in particular benzothiophene, dibenzothiophene, benzonaphthothiophene and their mono-or multi-substituted derivatives, more specifically 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene.

 By "desulfurization" is meant any treatment to reduce the sulfur content of the hydrocarbon mixture.

 The sulfur compounds can be oxidized, for example, to the corresponding sulfoxides, sulfones and sulfonic acids.

 By "nitrogen compounds" is meant all compounds present in the hydrocarbon mixture which contain nitrogen. These are in particular indole, carbazole, quinoline, acridine, aniline and their mono-or multi-substituted derivatives.

 By "denitrogenation" is meant any treatment to reduce the nitrogen content of the hydrocarbon mixture.

 Nitrogen compounds can be oxidized for example amine oxides, acridones, indigo and nitroso compounds or nitro.

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 The oxidizing agent used in the process according to the invention may be chosen from gaseous oxygen, hydrogen peroxide, ozone, nitrogen oxides, nitric acid, organic peracids (carboxylic, sulphonic and phosphonic) or minerals (Caro acid, perboric acid), chlorine, mineral and organic hypochlorites, hydroperoxides and persalts (perborate, percarbonate). An oxidizing agent containing hydrogen peroxide is preferred. According to a first variant, the hydrogen peroxide can be used in the presence of a carboxylic acid (such as acetic acid) and an acid catalyst so as to form in situ the corresponding peracid (such as peracetic acid). ) which is the substance that oxidizes sulfur compounds and / or nitrogen compounds. This first variant is used in the co-pending French patent application of the applicant filed on 26.02. 2001 under number 01.02688, the contents of which are incorporated by reference in this patent application. According to a second variant, the hydrogen peroxide may be used in the presence of a solid catalyst whose active sites are activated by hydrogen peroxide so as to be able to oxidize the sulfur compounds and / or the nitrogen compounds. This second variant is used in the French patent application co-pending the plaintiff filed 09.05. 2001 under number 01. 06151, the contents of which are incorporated by reference in this patent application.

ou égale à 0 C, les températures supérieures ou égales à 10 C étant les plus avantageuses. La température est le plus souvent inférieure ou égale à 180 C, plus spécialement inférieure ou égale à 100 C et de préférence inférieure ou égale à 40 C. In the process according to the invention, the extraction step is generally carried out at a temperature greater than or equal to -10 C, in particular higher than

or equal to 0 C, the temperatures greater than or equal to 10 C being the most advantageous. The temperature is most often less than or equal to 180 ° C., more particularly less than or equal to 100 ° C. and preferably less than or equal to 40 ° C.

 In the process according to the invention, the extraction step is generally carried out at atmospheric pressure. Over or under atmospheric pressures are also suitable. Atmospheric pressure is preferred.

 In the process according to the invention, the oxidation step may be preceded by one or more other steps such as the conventional steps of a refining process. Particularly good results are obtained when the oxidation step is preceded by one or more hydrodesulfurization steps.

 In the process according to the invention, the oxidation and extraction steps may be separated by one or more other steps such as filtration,

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 aqueous washing, destruction of the residues of the oxidizing agent, adsorption, stripping or distillation.

 In the process according to the invention, it may be advantageous to recover, after extraction, the phase which contains the extraction solvent and the oxidized sulfur compounds and / or the oxidized nitrogen compounds, to subject it to a treatment of purification to remove the oxidized compounds and recycle the purified solvent to the extraction. This purification treatment may for example comprise distillation, precipitation, adsorption and chemical treatment steps.

 In the process according to the invention, in general the phase which contains the hydrocarbon mixture and solvent residues is recovered after extraction. In a first variant, this phase may be subjected to a treatment treatment to remove the solvent residues. This treatment treatment may for example be a distillation, stripping, washing with water or adsorption. In a second variant, the phase which contains the mixture of hydrocarbons and solvent residues may be subjected to one or more subsequent treatments. These include, on the one hand, conventional steps of a refining process such as hydrodesulfurization or cracking, and, on the other hand, distillation or adsorption steps. Particularly good results are obtained with one or more adsorption steps. In a third variant, the first variant is combined with the second variant, that is to say that the phase which contains the mixture of hydrocarbons and solvent residues is subjected initially to a purification treatment ( as in the first variant) and then to one or more subsequent treatments (as in the second variant).

 Good results are obtained when the oxidation step is preceded by one or more hydrodesulfurization steps, and / or the extraction step is followed by one or more hydrodesulfurization steps.

 In a particularly advantageous embodiment of the process according to the invention, the process is carried out continuously using the installation shown schematically in the figure, in the particular case where the extraction solvent is denser than the mixture of hydrocarbons resulting from of the oxidation step. In this installation, the oxidation reactor 1 is fed with an oxidizing agent (preferably an aqueous solution of hydrogen peroxide) via line 2, and a mixture of hydrocarbons containing sulfur compounds and / or compounds nitrogenized by the 3. In the oxidation reactor 1, the sulfur compounds and / or the nitrogen compounds are oxidized to sulfur compounds.

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 oxidized and / or oxidized nitrogen compounds (referred to as "oxidized compounds" in the following). Thus, two phases are formed in the reactor, a heavier aqueous phase containing the oxidizing agent and a lighter organic phase containing the hydrocarbon mixture as well as the oxidized compounds. The hydrocarbon mixture containing the oxidized compounds is withdrawn from the reactor 1 through the pipe 4 and transported to an extractor 5. The aqueous liquid phase is withdrawn from the reactor 1 through the pipe 6 to be recycled to the reactor 1 through the pipe 2. The system can be purged through Line 7.

Fresh extraction solvent is introduced into the extractor 5 via line 8.

Within the extractor 5, two liquid phases are formed, a heavier first phase which contains the extracted solvent and the oxidized compounds extracted, and a lighter second phase which contains the hydrocarbon mixture depleted in oxidized compounds and possibly traces of the solvent. The heavy phase leaves the extractor via line 9 and is transported to a separation zone 10 (for example a distillation column), which makes it possible to separate the oxidized compounds from the solvent. The oxidized compounds can be sent to other treatments via line 11. The purified solvent is recycled to the extractor 5 via line 12. The light phase formed in extractor 5, containing the mixture of hydrocarbons depleted in compounds oxidized and also containing solvent residues is withdrawn from the extractor 5 via the pipe 13 and transported in the tank 14 to remove the solvent residues. This vessel may be a distillation column, an adsorption column or a water washing column. The final product leaving the tank 14 via the line 15 constitutes the hydrocarbon mixture depleted of sulfur and / or nitrogen.

Examples
Two samples of hydrocarbon mixtures were used: - A sample of Straight Run Gas Oil (SRGO) - A sample of gas oil obtained by cracking and hydrotreated (Light Cycle Oil,
LCO)
The characteristics of these two sections are shown in Table 1.

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Table 1: Characteristics of Oil Mixture Samples

<Tb>
<tb> SRGO <SEP> LCO
<tb> [Aromatic] <SEP> by <SEP> HPLC <SEP> (IP <SEP> 391/95)
<tb> (% <SEP> wt)
<tb> Monoaromatic <SEP> 23.4 <SEP> 47.6
<tb> Di-aromatic <SEP> 3.5 <SEP> 24.2
<tb> Tri-aromatics <SEP> 0.3 <SEP> 4.7
<tb> TOTAL <SEP> 27.2 <SEP> 76.5
<tb> [S] <SEP> with <SEP> fluorescence <SEP> X <SEP> (XRF) <SEP> (wppm) <SEP> 39 <SEP> 1200
<tb> [S] <SEP> with <SEP> pyrofluorescence <SEP> (wppm) <SEP> 34
<tb> (combustion / fluo <SEP> UV)
<tb> [S] <SEP> by <SEP> Wickbold <SEP> (wppm) <SEP> 31
<tb> [N] <SEP> with <SEP> chemiluminescence <SEP> (wppm) <SEP> 12 <SEP> 524
<tb> [N <SEP> basic] <SEP> by <SEP> titration <SEP> (wppm) <SEP><0.1<SEP> 76
<tb> Density <SEP> to <SEP> 15 C <SEP> 0.8375 <SEP> 0.9205
<tb> ASTM <SEP> D86 <SEP> distillation <SEP> (C)
<tb> IBP <SEP> 203 <SEP> 179
<tb> 5 <SEP> vol% <SEP> 235 <SEP> 203
<tb> 10 <SEP> vol% <SEP> 248 <SEP> 210
<tb> 20 <SEP> vol% <SEP> 261 <SEP> 218
<tb> 30 <SEP> vol% <SEP> 270 <SEP> 229
<tb> 50 <SEP> vol% <SEP> 285 <SEP> 250
<tb> 60 <SEP> vol% <SEP> 292 <SEP> 265
<tb> 70 <SEP> vol% <SEP> 301 <SEP> 280
<tb> 80 <SEP> vol% <SEP> 312 <SEP> 301
<tb> 90 <SEP> vol% <SEP> 317 <SEP> 331
<tb> 95 <SEP> vol% <SEP> 339 <SEP> 351FBP <SEP> 348 <SEP> 359
<tb> Viscosity <SEP> to <SEP> 20 C <SEP> 3.58
<tb> Viscosity <SEP> to <SEP> 40 C <SEP> 3.42
<tb> Viscosity <SEP> to <SEP> 50 C1, <SEP> 901
<Tb>

Examples 1 and 2: Oxidation of hydrocarbon mixture samples
Example 1 Oxidation of SRGO
In a double jacketed Pyrex reactor equipped with a Teflon fluoropolymer and glass paddle stirrer, a point of introduction of nitrogen into the solution (bubbling), a refrigerant maintained at -25 ° C. of a system for adding a 38.5% w solution of hydrogen peroxide from a sample collection point, acetic acid (26.7070 g) is successively introduced into the reactor. ), sulfuric acid (0.7354 g) and SRGO

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 (284.440 g). 34 ml of the H 2 O 2 solution are then introduced at a rate of 50 ml / min using a metering pump; this operation constitutes the zero time of the reaction. The reaction medium is maintained at 25 ° C. for 1 h and then is brought to 50 ° C. for 5 hours. The color of the organic phase changes from yellow to orange. The phases are then separated and the organic phase is washed again with 3 times 25 ml of water. The analysis of the organic phase by vapor phase chromatography with specific detection of sulfur indicates a total conversion of the sulfur compounds present in the petroleum feedstock. The S content of the oxidized sample is 38 wppm by X-ray fluorescence.

Example 2 Oxidation of the LCO
In a double jacketed Pyrex reactor equipped with a Teflon fluoropolymer and glass paddle stirrer, a point of introduction of nitrogen into the solution (bubbling), a refrigerant maintained at -25 ° C. from a system for adding a 39.5% w solution of hydrogen peroxide from a sample collection point, acetic acid (25.8930 g) is successively introduced into the reactor. ), sulfuric acid (0.7250 g) and SRGO (274.130 g). 33 ml of the H 2 O 2 solution are then introduced at a rate of 50 ml / min using a metering pump; this operation constitutes the zero time of the reaction. The reaction medium is maintained at 25 ° C. for 1 h and then is brought to 50 ° C. for 5 hours. The color of the organic phase changes from yellow to brown. The phases are then separated and the organic phase is washed again with 3 times 25 ml of water. The analysis of the organic phase by vapor phase chromatography with specific detection of sulfur indicates a total conversion of the sulfur compounds present in the petroleum feedstock. The S content of the oxidized sample is 1277 wppm by X-ray fluorescence.

Examples 3 to 32: extraction of the SRGO sample before and after oxidation under different conditions
The mixture of hydrocarbons (30 to 50 ml) and the polar solvent are placed at 22 ° C. in a separating funnel and stirred vigorously. After decantation, the polar phase and the non-polar phase are separated. (The latter is centrifuged at 4000 rpm for 20 minutes for further decantation).

- 10/1 v/v : tableau 2 - 2 fois 10/1 v/v : tableau 3 - 3 fois 10/1 v/v : tableau 4 - 4 fois 10/1 v/v : tableau 5 The hydrocarbon mixture / solvent ratios used are:

- 10/1 v / v: Table 2 - 2 times 10/1 v / v: Table 3 - 3 times 10/1 v / v: Table 4 - 4 times 10/1 v / v: Table 5

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- 4/1 v / v: table 6
The S content in the hydrocarbon mixture is determined by X-ray fluorescence. For the extractions employing dimethylsulfoxide (DMSO), the hydrocarbon mixture is subjected to an aqueous washing (2 x the same volume) before assaying the S by X-ray fluorescence. The polar solvent contents of the hydrocarbon mixture are determined by vapor phase chromatographic analysis. The total S concentration of the extraction solvent phase is then calculated as the difference between the S contained in the initial hydrocarbon mixture and the hydrocarbon mixture after extraction - the partition coefficient of the S defined as the ratio between the mass concentration in S in the polar phase and in the mixture of hydrocarbons - the hydrocarbon mixture output after extraction defined as the ratio between the mass of the hydrocarbon mixture after extraction and the mass of the hydrocarbon mixture initially released implemented; this value is therefore calculated on the basis of the mixture of hydrocarbons containing residues of the extraction solvent the actual yield of hydrocarbon mixture corrected by the residual extraction solvent content - the percentage of S extracted (% S extract) defined as the percentage of moles of S having been removed from the hydrocarbon mixture by extraction; this value is somewhat different from the variation of the S content of the diesel phase (Difference [S]), which is influenced by the mutual extraction of solvent and petroleum hydrocarbons.

the efficiency factor K defined by Zannikos [Zannikos F., E. Laws, Stoumas S., Fuel Processing Technology, 1995, V 42, P 35-45] as the ratio between the% S extracted and the fraction of the mixture hydrocarbon lost by passage into the solvent phase; this quantity characterizes the selectivity of the extraction process
Examples 33 to 42: extraction of the LCO sample before and after oxidation under different conditions
The hydrocarbon mixture (30 to 50 mL) and the polar solvent are placed at 22 ° C in a separatory funnel and stirred vigorously. After decantation, the polar phase and the non-polar phase are separated. (The latter is centrifuged at 6000 rpm for 20 minutes for further decantation).

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The hydrocarbon mixture / solvent ratio used is 4/1 v / v (Table 7).

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Table 2: Extraction SRGO mixture of hydrocarbons / solvent = 10/1 v / v

<Tb>
<tb> Example <SEP> Solvent <SEP> [S] <SEP> mixture <SEP> [S] <SEP> solvent <SEP> Coefficient <SEP> of <SEP> Yield <SEP> [solvent] <SEP> Yield <SEP> fixed <SEP>% <SEP> S <SEP> excerpt <SEP> Difference <SEP> K
<tb> hydrocarbon <SEP> (ppm) <SEP> partition <SEP> S <SEP> mixture <SEP> in <SEP><SEP> (%) <SEP> [S] <SEP> (%) )
<tb> bures <SEP> (ppm) <SEP> of hydrocarb- <SEP> mixture
<tb> bures <SEP> (%) <SEP> of hydrocarbons <SEP> (g / kg)
<tb> Before <SEP> oxidation
<tb> 1 <SEP> * <SEP> Dimethylsulfoxide <SEP> (DMSO) <SEP> 39 <SEP> 0 <SEP> 0 <SEP> 100.1 <SEP> 4.3 <SEP> 99.7 <SEP > 0 <SEP> 0 <SEP> 0
<tb> 2 * <SEP> N, <SEP> N-dimethylformamide <SEP> 30 <SEP> 106 <SEP> 4 <SEP> 102.5 <SEP> 37.4 <SEP> 98.7 <SEP> 21 <SEP> 23 <SEP> 16
<tb> (DMF)
<tb> 3 <SEP> * <SEP>&gamma; -butyrolactone <SEP> 36 <SEP> 25 <SEP> 1 <SEP> 99.1 <SEP> 13 <SEP> 97.8 <SEP> 9 <SEP> 8 <SEP> 4
<tb> 4 * <SEP> acetonitrile <SEP> (MeCN) <SEP> 39-3 <SEP> 0 <SEP> 100.5 <SEP> 17 <SEP> 98, <SEP> 8-1 <SEP> 0 <SEP> 0
<tb> 5 <SEP> * <SEP> carbonate <SEP> of <SEP> 1,2-propylene <SEP> 37 <SEP> 17 <SEP> 0 <SEP> 98.8 <SE> 2.5 <SEP > 98.6 <SEP> 6 <SEP> 5 <SEP> 4
<tb> 6 <SEP> * <SEP> adiponitrile <SEP> 37 <SEP> 21 <SEP> 1 <SEP> 98.7 <SEP> 0.7 <SEP> 98.6 <SEP> 6 <SEP> 5 <SEP> 5
<tb> * <SEP> examples <SEP> no <SEP> compliant <SEP> to <SEP> the invention
<Tb>

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Table 2 (continued)

<Tb>
<tb> Example <SEP> Solvent <SEP> [S] <SEP> mixture <SEP> [S] <SEP> solvent <SEP> Coefficient <SEP> Yield <SEP> [solvent] <SEP> Yield <SEP> corrected <SEP>% <SEP> S <SEP> excerpt <SEP> Difference <SEP> K
<tb> hydrocarbon <SEP> (ppm) <SEP> of <SEP> partition <SEP> mixture <SEP> in <SEP><SEP> (%) <SEP> [S] <SEP> (% )
<tb> bures <SEP> (ppm) <SEP> S <SEP> of hydrocarb- <SEP> mixture
<tb> bures <SEP> (%) <SEP> of hydrocarbons
<tb> (g / kg)
<tb> After <SEP> oxidation
<tb> 7DMSO <SEP> 17 <SEP> 176 <SEP> 10 <SEP> 98.2 <SEP> 4.4 <SEP> 97, <SEP> 8 <SEP> 57 <SEP> 56 <SEP> 26
<tb> 8 <SEP> * <SEP> DMF <SEP> 14 <SEP> 306 <SEP> 22 <SEP> 101.6 <SEP> 45.7 <SEP> 97.0 <SE> 64 <SEP> 64 <SEP> 21
<tb> 9 * <SEP> y-butyrolactone <SEP> 16 <SEP> 182 <SEP> 11 <SEP> 99.0 <SEP> 16.0 <SEP> 97, <SEP> 5 <SEP> 59 <SEP > 59 <SEP> 23
<tb> 10 <SEP> * <SEP> MeCN <SEP> 27, <SEP> 7 <SEP> 158 <SEP> 6 <SEP> 99.6 <SEP> 19.0 <SEP> 97.7 <SEP> 29 <SEP> 29 <SEP> 13
<tb> 11 <SEP> carbonate <SEP> of <SEP> 1,2-propylene <SEP> 18 <SEP> 147 <SEP> 8 <SEP> 99, <SEP> 0 <SEP> 2,7 <SEP> 98.7 <SEP> 54 <SEP> 54 <SEP> 42
<tb> 12 <SEP> adiponitrile <SEP> 19 <SEP> 194 <SEP> 10 <SEP> 97, <SEP> 9 <SEP> 0.9 <SEP> 97.9 <SEP> 52 <SEP> 51 <SEP> 24
<Tb>
* examples not in accordance with the invention

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Table 3: Extraction SRGO mixture of hydrocarbons / solvent = 2 times 10/1 v / v

<Tb>
<tb> Example <SEP> Solvent <SEP> [S] <SEP> mixture <SEP> [S] <SEP> solvent <SEP> Coefficient <SEP> of <SEP> Yield <SEP> [solvent] <SEP> in <SEP> Yield <SEP> Corrected <SEP>% <SEP> S <SEP> Extracted <SEP> Difference <SEP> K
<tb> hydrocarbons <SEP> (ppm) <SEP> partition <SEP> S <SEP> mixture <SEP><SEP> mixture <SEP> (%) <SEP> [S] <SEP> (%)
<tb> (ppm) <SEP> of hydrocarbons of hydrocarbons <SEP> (%) <SEP> carbides <SEP> (g / kg)
<tb> After <SEP> oxidation
<tb> 13 <SEP> * <SEP> DMSO <SEP> 11 <SEP> 44 <SEP> 4 <SEP> 99.0 <SEP> 4, <SEP> 4 <SEP> 98, <SEP> 6 <SEP > 72 <SEP> 72 <SEP> 52
<tb> 14 <SEP> * <SEP> DMF <SEP> 7 <SEP> 47 <SEP> 7 <SEP> 99, <SEP> 4 <SEP> 45.7 <SEP> 94.8 <SE> 82 <SEP> 82 <SEP> 16
<tb> 15 <SEP> * <SEP> y-butyrolactone <SEP> 8 <SEP> 55 <SEP> 7 <SEP> 98.8 <SEP> 16.0 <SEP> 97.2 <SE> 80 <SEP > 79 <SEP> 28
<tb> 16 <SEP> carbonate <SEP> of <SEP> 1, <SEP> 2- <SEP> 14 <SEP> 28 <SEP> 2 <SEP> 98, <SEP> 6 <SEP> 2.7 <SEP> 98.3 <SEP> 65 <SEP> 64 <SEP> 38
<tb> propylene
<tb> 17 <SEP> Adiponitrile <SEP> 16 <SEP> 23 <SEP> 1 <SEP> 98, <SEP> 3 <SEP> 0.9 <SEP> 98.2 <SEP> 60 <SEP> 59 <SEP> 34
<Tb>
* examples not in accordance with the invention

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Table 4: Extraction SRGO mixture of hydrocarbons / solvent = 3 times 10/1 v / v

<Tb>
<tb> Example <SEP> Solvent <SEP> [S] <SEP> mixture <SEP> [S] <SEP> solvent <SEP> Coefficient <SEP> of <SEP> Yield <SEP> mixture <SEP> [solvent] <SEP> in <SEP> Yield <SEP> Corrected <SEP>% <SEP> S <SEP> Extracted <SEP> Difference <SEP> K
<tb> hydrocarbons <SEP> (ppm) <SEP> partition <SEP> S <SEP> of hydrocarbon <SEP> mixture <SEP> (%) <SEP> [S] <SEP> (%)
<tb> (ppm) <SEP> bures <SEP> (%) <SEP> of hydrocarbons <SEP> (g / kg)
<tb> After <SEP> oxidation
<tb> 18 <SEP> * <SEP> DMSO <SEP> 8 <SEP> 23 <SEP> 3 <SEP> 98.9 <SEP> 4.4 <SEP> 98.4 <SE> 80 <SEP> 79 <SEP> 51
<tb> 19 * DMF10-76-8 <SEP> 98.9 <SEP> 45.7 <SEP> 94.4 <SEP> 75 <SEP> 74 <SEP> 13
<tb> 20 <SEP> * <SEP> y-butyrolactone <SEP> 5 <SEP> 21 <SEP> 4 <SEP> 98.2 <SEP> 16.0 <SEP> 96.7 <SEP> 87 <SEP > 87 <SEP> 26
<tb> 21 <SEP> carbonate <SEP> of <SEP> 1, <SEP> 2- <SEP> 10 <SEP> 28 <SEP> 3 <SEP> 98, <SEP> 4 <SEP> 2.7 <SEP> 98.1 <SEP> 75 <SEP> 74 <SEP> 40
<tb> propylene
<tb> 22 <SEP> Adiponitrile <SEP> 10 <SEP> 52 <SEP> 5 <SEP> 98, <SEP> 2 <SEP> 0.9 <SEP> 98.1 <SEP> 75 <SEP> 74 <SEP> 39
<Tb>
* examples not in accordance with the invention

<Desc / Clms Page number 17>

Table 5: Extraction SRGO mixture of hydrocarbons / solvent = 4 times 10/1 v / v

<Tb>
<tb> Example <SEP> Solvent <SEP> [S] <SEP> mixture <SEP> [S] <SEP> solvent <SEP> Coefficient <SEP> of <SEP> Yield <SEP> [solvent] <SEP> in <SEP> Yield <SEP> Corrected <SEP>% <SEP> S <SEP> Extracted <SEP> Difference <SEP> K
<tb> hydrocarbons <SEP> (ppm) <SEP> partition <SEP> S <SEP> mixture <SEP><SEP> mixture <SEP> (%) <SEP> [S] <SEP> (%)
<tb> (ppm) <SEP> of hydrocarbhydrocarbubures <SEP> (%) <SEP> res <SEP> (g / kg)
<tb> After <SEP> oxidation
<tb> 23 <SEP> * <SEP> DMSO <SEP> 6 <SEP> -57 <SEP> -9 <SEP> 98.5 <SEP> 4, <SEP> 4 <SEP> 98.1 <SEP> 85 <SEP> 85 <SEP> 45
<tb> 24 <SEP> * <SEP> DMF <SEP> 10 <SEP> 58 <SEP> 6 <SEP> 96, <SEP> 1 <SEP> 45.7 <SEP> 91, <SEP> 7 <SEP > 75 <SEP> 74 <SEP> 9
<tb> 25 <SEP> * <SEP> y-butyrolactone <SEP><5<SEP> 35 <SEP> 97, <SEP> 3 <SEP> 16.0 <SEP> 95.7 <SEP> 100 <SEP > 100 <SEP> 23
<tb> 26 <SEP> carbonate <SEP> of <SEP> 1, <SEP> 2- <SEP> 7 <SEP> 21 <SEP> 3 <SEP> 98.2 <SEW> 2.7 <SEP> 97 , <SEP> 9 <SEP> 82 <SEP> 82 <SEP> 40
<tb> propylene
<tb> 27 <SEP> Adiponitrile <SEP> 8 <SEP> 18 <SEP> 2 <SEP> 97.7 <SEP> 0.9 <SEP> 97.6 <SEP> 80 <SEP> 79 <SEP> 34
<Tb>
* examples not in accordance with the invention

<Desc / Clms Page number 18>

Table 6: Extraction SRGO mixture of hydrocarbons / solvent = 4/1 v / v

<Tb>
<tb> Example <SEP> Solvent <SEP> [S] <SEP> mixture <SEP> [S] <SEP> solvent <SEP> Coefficient <SEP> of <SEP> Yield <SEP> [solvent] <SEP> in <SEP> Yield <SEP> Corrected <SEP>% <SEP> S <SEP> Difference <SEP> K
<tb> hydrocarbons <SEP> (ppm) <SEP> partition <SEP> S <SEP> mixture <SEP> the <SEP> mixture <SEP> (%) <SEP> extract <SEP> [S] <SEP > (%)
<tb> (ppm) <SEP> of hydrocarbhydrocarbubures <SEP> (%) <SEP> res <SEP> (g / kg)
<tb> After <SEP> oxidation
<tb> 28 <SEP> * <SEP> DMSO <SEP> 12 <SEP> 82 <SEP> 7 <SEP> 99.0 <SEP> 4.4 <SEP> 98.6 <SE> 70 <SEP> 69 <SEP> 50
<tb> 29 <SEP> * <SEP> DMF <SEP> 8 <SEP> 109 <SEP> 14 <SEP> 99.3 <SEP> 45.7 <SEP> 94.7 <SEP> 80 <SEP> 79 <SEP> 15
<tb> 30 * y-butyrolactone <SEP> 8 <SEP> 86 <SEP> 11 <SEP> 98.2 <SEP> 16.0 <SEP> 96.6 <SE> 80 <SE> 79 <SEP> 24
<tb> 31 <SEP> carbonate <SEP> of <SEP> 1, <SEP> 2- <SEP> 13 <SEP> 71 <SEP> 5 <SEP> 98.4 <SEP> 2.7 <SEP> 98 , 1 <SEP> 67 <SEP> 67 <SEP> 36
<tb> propylene
<tb> 32 <SEP> Adiponitrile <SEP> 14 <SEP> 85 <SEP> 6 <SEP> 97.8 <SEP> 0, <SEP> 9 <SEP> 97, <SEP> 7 <SEP> 65 <SEP > 64 <SEP> 28
<Tb>
* examples not in accordance with the invention

<Desc / Clms Page number 19>

Table 7: Extraction LCO hydrocarbon mixture / solvent = a 4/1 v / v extraction

<Tb>
<tb> Example <SEP> Solvent <SEP> [S] <SEP> mixture <SEP> [S] <SEP> solvent <SEP> Coefficient <SEP> of <SEP> Yield <SEP> mixture <SEP> [solvent] <SEP> in <SEP> Yield <SEP> Corrected <SEP>% <SEP> S <SEP> Extracted <SEP> Difference <SEP> K
<tb> hydrocarbons <SEP> (ppm) <SEP> partition <SEP> S <SEP> of hydrocarbons <SEP> the <SEP> mixture <SEP> (%) <SEP> [S] <SEP> ( %)
<tb> (ppm) <SEP> (%) <SEP> of hydrocarbons <SEP> (g / kg)
<tb> Before <SEP> oxidation
<tb> 33 <SEP> * <SEP> DMSO <SEP> 1100 <SEP> 458, <SEP> 2 <SEP> 0, <SEP> 4 <SEP> 94.7 <SEP> 54, <SEP> 4 <SEP> 89, <SEP> 6 <SEP> 13 <SEP> 8 <SEP> 1, <SEP> 3
<tb> 34 <SEP> DMF <SEP> Miscibility
<tb> complete <SEP> of
<tb> two <SEP> phases
<tb> 35 <SEP> * <SEP> y-butyrolactone <SEP> 920 <SEP> 921, <SEP> 7 <SEP> 1, <SEP> 0 <SEP> 79, <SEP> 6 <SEP> 77, <SEP> 8 <SEP> 73.4 <SEP> 39 <SEP> 23 <SEP> 1.5
<tb> 36 <SEP> * <SEP> carbonate <SEP> of <SEP> 1, <SEP> 2- <SEP> 1100 <SEP> 457.2 <SEP> 0.4 <SEP> 92.8 <SEP > 23.4 <SEP> 90.6 <SEP> 15 <SEP> 8 <SEP> 1.6
<tb> propylene
<tb> 37 <SEP> * <SEP> Adiponitrile <SEP> 1200 <SEP> 288, <SEP> 8 <SEP> 0, <SEP> 2 <SEP> 92, <SEP> 1 <SEP> 17, <SEP > 2 <SEP> 90.6 <SEP> 8 <SEP> 0 <SEP> 0, <SEP> 8
<tb> After <SEP> oxidation
<tb> 38 <SEP> * <SEP> DMSO <SEP> 465 <SEP> 2008 <SEP> 4 <SEP> 90, <SEP> 7 <SEP> 52, <SEP> 6 <SEP> 86, <SEP> 0 <SEP> 65 <SEP> 61 <SEP> 4, <SEP> 6
<tb> 39 <SEP> * <SEP> DMF <SEP> Miscibility
<tb> complete <SEP> of
<tb> two <SEP> phases
<tb> 40 <SEP> * <SEP> y-butyrolactone <SEP> 345 <SEP> 1619 <SEP> 5 <SEP> 72, <SEP> 1 <SEP> 72, <SEP> 1 <SEP> 66, <SEP> 9 <SEP> 79 <SEP> 71 <SEP> 2, <SEP> 4
<tb> 41 <SEP> carbonate <SEP> of <SEP> 1, <SEP> 2- <SEP> 500 <SEQ> 1774 <SEP> 4 <SEP> 89, <SEP> 2 <SEP> 23.9 <MS> 87.1 <SEP> 63 <SEP> 58 <SEP> 4.9
<tb> propylene
<tb> 42 <SEP> adiponitrile <SEP> 555 <SEP> 1961 <SEP> 4 <SEP> 89, <SEP> 4 <SEP> 15, <SEP> 9 <SEP> 88, <SEP> 0 <SEP> 59 <SEP> 54 <SEP> 4, <SEP> 9
<Tb>
* examples not in accordance with the invention

Claims (10)

1-Process for the desulfurization and / or denitrogenation of a hydrocarbon mixture containing sulfur-containing compounds and / or nitrogen-containing compounds, comprising an oxidation step by means of an oxidizing agent in order to oxidize the sulfur compounds and / or the nitrogenous compounds, followed by a step of extracting the oxidized sulfur compounds and / or oxidized nitrogen compounds by means of an extraction solvent, characterized in that the extraction solvent contains adiponitrile and / or or 1,2-propylene carbonate.  2-Process according to claim 1, characterized in that the hydrocarbon mixture contains hydrocarbons containing 10 or more carbon atoms in an amount of greater than 50% by weight.  3-Process according to claim 1 or 2, characterized in that the oxidizing agent contains hydrogen peroxide.  4-Process according to any one of claims 1 to 3, characterized in that the extraction step is carried out continuously.  5-Process according to claim 4, characterized in that the extraction solvent is used in an amount such that the ratio of flow rates entering the extraction device of the hydrocarbon mixture from the oxidation step and the solvent is at least 0.1 and at most 100.  6-Process according to any one of claims 1 to 5, characterized in that the hydrocarbon mixture contains aromatic hydrocarbons in an amount of at most 80% by weight.  7-Process according to any one of claims 1 to 6, characterized in that the sulfur compounds are selected from benzothiophene, dibenzothiophene, benzonaphthothophene and their mono-or multi-substituted derivatives.  8-Process according to any one of claims 1 to 7, characterized in that the nitrogen compounds are chosen from indole, carbazole, quinoline, acridine, aniline and their mono-or multi-substituted derivatives. <Desc / Clms Page number 21>  9-Process according to any one of claims 1 to 8, characterized in that the extraction solvent also contains water in an amount of at least 0.1% by weight and at most 5% by weight. weight.  10-Process according to any one of claims 1 to 9, characterized in that the oxidation step is preceded by one or more hydrodesulfurization steps, and / or the extraction step is followed by a or several hydrodesulfurization steps.