EP1397468A1 - Method of refining crude oils having high organic acidity - Google Patents

Method of refining crude oils having high organic acidity

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Publication number
EP1397468A1
EP1397468A1 EP02743342A EP02743342A EP1397468A1 EP 1397468 A1 EP1397468 A1 EP 1397468A1 EP 02743342 A EP02743342 A EP 02743342A EP 02743342 A EP02743342 A EP 02743342A EP 1397468 A1 EP1397468 A1 EP 1397468A1
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EP
European Patent Office
Prior art keywords
compound
formula
chosen
crude oil
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP02743342A
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German (de)
French (fr)
Inventor
Paul Maldonado
Roland Barberet
Louis Genevois
Alain Catros
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Total Marketing Services SA
Original Assignee
Total France SA
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Publication date
Application filed by Total France SA filed Critical Total France SA
Publication of EP1397468A1 publication Critical patent/EP1397468A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • C10G21/20—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20—Organic compounds not containing metal atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline

Definitions

  • the present invention relates to a process for refining crude oils with high organic acidity.
  • Crude oils or fractions thereof having high acid contents are mainly those containing naphthenic acids. It is known that these crude oils present risks of corrosion both during their extraction from the oil field, during their transportation and during their refining. Oil tankers and refiners must find ways to recover these crude oils without being forced to develop new technologies to protect devices and equipment for transporting these crude oils or their fractions or for processing them. whether in the field, in shipping or rail, in pipes or in the refinery. This acidity of crude oils is conventionally measured by the number or index of TAN (Total Acid Number), which is measured in accordance with standard ASTM D664 by potentiometry and standard D974 by colorimetry. So, we apply a.
  • TAN Total Acid Number
  • US-P-2769768 describes the use of a linear or branched primary alcohol having from 4 to 7 carbon atoms with a mixture formed of methanol and ammonia to neutralize and remove heavy naphthenic acids from a hydrocarbon oil dewaxed.
  • Patent US-3176041 proposes to trap the naphthenic acids of a crude oil by contact with a clay impregnated with a volatile amine having a boiling point below 100 ° C., in particular ammonia. This process is not applicable on the crude oil production field, nor even in a refinery because it requires a contact temperature above 200 ° C for 20 to 75 minutes and the extremely complex daily regeneration of several hundred tonnes of clay .
  • US-P-2911360 describes a process applying to crude oil.
  • the crude oil is deacidified in the liquid phase by contacting with a base in the presence of an alcohol, then distilled.
  • the base can be ammonia, while the next phase is an aqueous solution containing 30 to 50% by weight of alcohol.
  • the naphthenic acids recovered by distillation are regenerated after acidification with sulfuric acid of the extraction solvent. This process is cumbersome because it involves two treatments, one in the liquid phase and the other in the vapor phase. Furthermore, it is only applicable in a refinery, since it includes atmospheric distillation and vacuum distillation of the treated crude oil.
  • US-P-4634519 describes a process for deacidifying petroleum fractions using a specific solvent mixture, comprising water, methanol and ammonia. It is a question here of extracting naphthenic acids. This process applies to petroleum fractions only, since the application of this treatment to crude oil has led to a stable emulsion making recovery of the extraction solvent almost impossible.
  • the object of the present invention is to convert into amides, the organic acids contained in a crude oil with high acidity, mainly the acids naphthenic, during a conventional refining of this crude oil in a refinery.
  • the distilled fractions thus neutralized are no longer the cause of major corrosion phenomena in the equipment crossed.
  • these cuts can even be valued, this treatment having the effect of promoting the appearance of amide functions improving the quality of the products sold. It is thus possible to limit the addition of lubricating additives in gasolines and middle distillates, kerosene and diesel, this lubricating function being in fact already present within the distilled cut.
  • the present invention therefore relates to a process for refining by neutralization of the organic acidity of crude oils with high acidity consisting in adding a nitrogenous compound to said crude oil, said process being characterized in that one introduces in at least one point of the petroleum pretreatment unit upstream of, or in the atmospheric distillation unit, a nitrogenous compound comprising at least three carbon atoms, a secondary amino group and a hydroxyl group.
  • a nitrogenous compound comprising at least three carbon atoms, a secondary amino group and a hydroxyl group.
  • the amine salts resulting from the naphthenic acids remain in the crude oil both during the crude oil preheating operations and during the desalting operations, gradually transforming into amides. Thus, they are always present but in the amide form in the crude oil when it enters the atmospheric distillation furnace.
  • the amidified naphthenic acids and the other amides possibly formed from other acidic compounds present are distilled like the other hydrocarbons and are found in the various cuts usually distilled. It is advantageously found that these amides give the distilled cuts unexpected properties of lubricity and anticorrosion. Thus, it was thus found that at the head of the tower it was possible to limit or even eliminate the addition of neutralizing amines.
  • cuts of middle distillates for the production of diesel have very low acidity and improved lubricity.
  • the nitrogen compounds used are chosen from the compounds of formula (I) below: Y - OH
  • IZ in which Y is a linear or branched alkyl group comprising from 1 to 10 carbon atoms, optionally hydroxylated, and Z is chosen from alkyl, hydroxyalkyl and polyhydroxyalkyl groups (containing up to 6, preferably up to 4 hydroxy), primary and secondary amines or tertiary and their hydroxylated and polyhydroxylated derivatives, the alkyl functions of these groups comprising from 1 to 10 carbon atoms.
  • a compound of formula (I) in which Z is a group chosen from hydroxyalkyl and polyhydroxyalkyl groups are chosen from the dialkanolamines from the group consisting of diethanolamine, dipropanolamine, dibutanolamine, N-propanol-2-ethanolamine, N-butanol-2-ethanolamine, N - butanol-3-ethanolamine, N-butanol-2-propanolamine, N-butanol-3-propanolamine, N-propanol-2-butanolamine, di- (methyl1-hydroxy2) - propylamine, diisopropanolamine and di - (méthyl2hydroxy2) -butylamine.
  • the preferred compounds are chosen from diethanolamine and diisopropanolamine.
  • the compounds of formula (I) are chosen from N-methyl-ethanolamine, N-propyl-ethanoiamine, N-butylethanolamine, N-isobutylethanolamine, N-pentylethanolamine, N-methyl-propanolamine, N-isopentylethanolamine, N-propyl-propanolamine, N-butylpropanolamine, N-isobutylpropanolamine, N-pentylpropanolamine, N-isopentylpropanolamine, N-methyl-butanolamine, N-propyl-butanolamine, N-butylbutanolamine, N-isobutyl -butanolamine, N-pentylbutanolamine, N-isopentylbutanolamine, N-methyl-pentanolamine, N-propyl-pentanolamine, N-butylpentanolamine, N-isopentylbut
  • the preferred compounds of this third mode are chosen from the group consisting of N-Hydroxy-2-ethylhydrazine, N-hydroxy-2-ethylethylenediamine, N-hydroxy-2-ethyl- (1-3) propylenediamine, N , N'-bis (2,3-dihydroxy-propyl) amine and hydroxy-2- (1, 3) propylenediamine.
  • N-hydroxy-2-ethylethylenediamine will be chosen.
  • the compound of formula (I) can be introduced before the crude oil desalination unit, in the preheating train of desalted crude oil, preferably before the exchangers or else in the distillation tower.
  • Another object of the invention is the application of the process for the neutralization of organic acids contained in crude oils with an acidity greater than 0.5 mg KOH / g.
  • a third object of the invention corresponds to the petroleum fractions obtained by application of said method according to the first object of the invention.
  • a second type of cut corresponds to the so-called light cuts of cut temperature between the initial point and 150 ° C. and of acidity less than 0.5 mg of KOH / g.
  • the present example describes the process for transforming organic acids in crude petroleum with the nitrogen compounds according to the invention.
  • the purpose of the present example is to describe the advantages linked to the process with regard to the improvement of the lubricity of middle distillate cuts and the anticorrosion effect of the amides formed in light distillation cuts.
  • Example I The 230-350 ° C sections of Example I are therefore taken up again with and without amidation before distillation and the lubricity is measured on each of them by the method known as HFRR (High Frequency Reciprocating Ring), according to standard EC12156-1. It is expressed in wear diameter (WSR: Wear Scare Diameter) in ⁇ m. Correct lubrication leads to wear diameter values of less than 460 ⁇ m. The lower this value, the better the lubricity.
  • WSR Wear Scare Diameter
  • the present example aims to show the progressive nature of the reaction of the alkanolamines in particular of diethanolamine (DEA) on crude oil B with an acidity corresponding to a TAN of 4.47 or 68 mmol / l of acidity measured.
  • DEA diethanolamine
  • reaction is followed within the crude oil during the addition of DEA by IRFT spectrometry using a measuring rod immersed in crude oil B forming part of the REACT IR spectrometer sold by the company METTLER.
  • Figures 1 and 2 give a representation of the evolution of the infrared spectra during the addition of DEA and during heating as a function of time.
  • Figure 1 shows, in three dimensions, the disappearance of the acid derivatives (band centered on the wavelength 1710 cm “1 ), the appearance of amine salts (band centered on 1560 cm “ 1 ) and the appearance amides (strip centered on 1650 cm “1 ).
  • FIG. 2 represents, in two dimensions, as a function of time, the formation of amide (band centered on 650 cm ⁇ 1 ) after addition of DEA and the maintenance of crude oil B for one hour at 140 ° C.
  • the formation of esters in small quantities linked to the presence of water supplied by the addition of DEA (band centered on 1740 cm ⁇ 1 ).

Abstract

The invention relates to a method of refining crude oils having high acidity by neutralising the organic acidity thereof. The inventive method consists in adding a nitrogenous compound to the crude oil. Said method is characterised in that a nitrogenous compound containing at least three carbon atoms, a secondary amine group and a hydric group is introduced at at least one point of the crude oil pre-treatment units upstream of, or in the atmospheric distillation unit.

Description

PROCEDE DE RAFFINAGE DE PETROLES BRUTS PROCESS FOR REFINING CRUDE OILS
A ACIDITE ORGANIQUE ELEVEEWITH HIGH ORGANIC ACIDITY
La présente invention concerne un procédé de raffinage des pétroles bruts à acidité organique élevée.The present invention relates to a process for refining crude oils with high organic acidity.
Les pétroles bruts ou des fractions de ceux-ci ayant des teneurs élevées en acide sont principalement ceux contenant des acides naphténiques. On sait que ces pétroles bruts présentent des risques de corrosion aussi bien lors de leur extraction sur champ pétrolifère, de leur transport que lors du raffinage de ceux-ci. Les pétroliers comme les raffineurs doivent trouver des moyens de valoriser ces pétroles bruts sans être obligés de développer de nouvelles technologies pour protéger des dispositifs et des équipements de transport de ces pétroles bruts ou de fractions de ceux-ci ou encore de traitement de ceux-ci que ce soit sur champ, dans les transports maritimes ou par chemin de fer, dans les pipes ou dans la raffinerie. Cette acidité des pétroles bruts est classiquement mesurée par le nombre ou indice de TAN (Total Acid Number), qui est mesuré conformément à la norme ASTM D664 par potentiomètrie et à la norme D974 par colorimétrie. Ainsi, on applique une. décote aux pétroles bruts en fonction de l'indice TAN: de la valeur de cette acidité dépend le prix du pétrole brut. Or, aujourd'hui la plupart des pétroles bruts extraits sont acides par nature, c'est-à-dire qu'ils contiennent des composés corrosifs comme les dérivés soufrés mais aussi des acides naphténiques. On comprend pourquoi la mise au point d'un procédé de traitement de ces pétroles bruts permettant d'obtenir une faible acidité dans la totalité du pétrole brut ou dans les différentes coupes carbonées le composant serait avantageuse : elle permettrait aussi bien d'accroître les marges de raffinage que de limiter les risques de corrosion générateur de dépenses supplémentaires en cas de percement des équipements, de stockage, de transport ou de traitement, notamment en raffineries. De nombreux efforts ont été faits ces dernières années afin de développer un tel procédé de désacidification ou de neutralisation des pétroles bruts. Parmi les différentes voies retenues, la neutralisation par des composés azotés, associée ou non à l'utilisation d'un solvant, a été particulièrement mentionnée dans les brevets US-P-2769768, US-3176041 , US-P-2911360, US-P- 4634519 ou US-P-5550296 .Crude oils or fractions thereof having high acid contents are mainly those containing naphthenic acids. It is known that these crude oils present risks of corrosion both during their extraction from the oil field, during their transportation and during their refining. Oil tankers and refiners must find ways to recover these crude oils without being forced to develop new technologies to protect devices and equipment for transporting these crude oils or their fractions or for processing them. whether in the field, in shipping or rail, in pipes or in the refinery. This acidity of crude oils is conventionally measured by the number or index of TAN (Total Acid Number), which is measured in accordance with standard ASTM D664 by potentiometry and standard D974 by colorimetry. So, we apply a. discount to crude oils according to the TAN index: the value of this acidity depends on the price of crude oil. However, today most of the crude oils extracted are acid by nature, that is to say that they contain corrosive compounds such as sulfur derivatives but also naphthenic acids. We understand why the development of a process for treating these crude oils making it possible to obtain low acidity in all of the crude oil or in the various carbonaceous cuts that make it up would be advantageous: it would also allow margins to be increased refining than limiting the risk of corrosion, generating additional costs in the event of piercing of equipment, storage, transport or processing, particularly in refineries. Many efforts have been made in recent years to develop such a deacidification or neutralization process for crude oils. Among the different routes chosen, neutralization with nitrogen compounds, associated or not with the use of a solvent, has been particularly mentioned in patents US-P-2,769,768, US-3,176,041, US-P-2,911,360, US- P- 4634519 or US-P-5550296.
Le brevet US-P-2769768 décrit l'utilisation d'un alcool primaire linéaire ou ramifié ayant de 4 à 7 atomes de carbone avec un mélange formé de méthanol et d'ammoniac pour neutraliser et enlever les acides naphténiques lourds d'une huile hydrocarbure déparaffinée. Le brevet US-3176041 propose de piéger les acides naphténiques d'un pétrole brut par contact avec une argile imprégnée par une aminé volatile ayant un point d'ébullition inférieur à 100°C, notamment de l'ammoniaque. Ce procédé n'est pas applicable sur champ de production de pétrole brut, ni même en raffinerie car il nécessite une température de contact supérieure à 200°C pendant 20 à 75 minutes et la régénération journalière extrêmement complexe de plusieurs centaines de tonnes d'argile.US-P-2769768 describes the use of a linear or branched primary alcohol having from 4 to 7 carbon atoms with a mixture formed of methanol and ammonia to neutralize and remove heavy naphthenic acids from a hydrocarbon oil dewaxed. Patent US-3176041 proposes to trap the naphthenic acids of a crude oil by contact with a clay impregnated with a volatile amine having a boiling point below 100 ° C., in particular ammonia. This process is not applicable on the crude oil production field, nor even in a refinery because it requires a contact temperature above 200 ° C for 20 to 75 minutes and the extremely complex daily regeneration of several hundred tonnes of clay .
Le brevet US-P-2911360 décrit un procédé s'appliquant à un pétrole brut. Le pétrole brut est désacidifié en phase liquide par mise en contact avec une base en présence d'un alcool, puis distillé. La base peut être l'ammoniaque, tandis que la phase suivante est une solution aqueuse contenant de 30 à 50% en poids d'alcool. Les acides naphténiques récupérées par distillation sont régénérés après acidification à l'acide sulfurique du solvant d'extraction. Ce procédé est lourd car il implique deux traitements, l'un en phase liquide et l'autre en phase vapeur. De plus il n'est applicable qu'en raffinerie, car il englobe la distillation atmosphérique et la distillation sous vide du pétrole brut traité.US-P-2911360 describes a process applying to crude oil. The crude oil is deacidified in the liquid phase by contacting with a base in the presence of an alcohol, then distilled. The base can be ammonia, while the next phase is an aqueous solution containing 30 to 50% by weight of alcohol. The naphthenic acids recovered by distillation are regenerated after acidification with sulfuric acid of the extraction solvent. This process is cumbersome because it involves two treatments, one in the liquid phase and the other in the vapor phase. Furthermore, it is only applicable in a refinery, since it includes atmospheric distillation and vacuum distillation of the treated crude oil.
Le brevet US-P-4634519 décrit un procédé de désacidification de coupes pétrolières utilisant un mélange solvant spécifique, comprenant de l'eau, du méthanol et de l'ammoniaque. Il s'agit ici d'extraire les acides naphténiques. Ce procédé s'applique à des coupes pétrolières uniquement, car l'application de ce traitement à un pétrole brut a conduit à une émulsion stable rendant la récupération du solvant d'extraction quasiment impossible.US-P-4634519 describes a process for deacidifying petroleum fractions using a specific solvent mixture, comprising water, methanol and ammonia. It is a question here of extracting naphthenic acids. This process applies to petroleum fractions only, since the application of this treatment to crude oil has led to a stable emulsion making recovery of the extraction solvent almost impossible.
Le brevet US-P-5550296 décrit la synthèse de cétones, mais décrit aussi un procédé de désacidification de pétrole brut directement à la sortie du puits sur un champ pétrolier, avant stabilisation du pétrole brut, par de l'ammoniac liquide pour neutraliser les acides naphténiques. Un tel procédé est impraticable tel quel en raffinerie.US-P-5550296 describes the synthesis of ketones, but also describes a process for deacidifying crude oil directly at the outlet of the well on an oil field, before stabilization of the crude oil, with liquid ammonia to neutralize acids naphthenic. Such a process is impractical as such in a refinery.
Pour le traitement spécifique de coupes pétrolières de type de celles obtenues par raffinage de pétrole brut, prises séparément, il a souvent été proposé d'utiliser des composés azotés de type monoalkyl ou monoarylamine, éventuellement des polymères de ces aminés, de monoalkanolamine, et même d'hydroxyde d'ammonium tétraalkylé comme il est décrit dans les brevets US -P-4589979, US-P- 4752381 , US-P-4827033, US-P-5683626 et EP 0924286A2.For the specific treatment of petroleum fractions of the type of those obtained by refining crude oil, taken separately, it has often been proposed to use nitrogen compounds of the monoalkyl or monoarylamine type, optionally polymers of these amines, of monoalkanolamine, and even of tetraalkylated ammonium hydroxide as described in patents US -P-4589979, US-P- 4752381, US-P-4827033, US-P-5683626 and EP 0924286A2.
Aucun des documents ci-dessus n'enseigne ni ne suggère l'invention qui ici s'applique essentiellement au pétrole brut non encore distillé.None of the above documents teaches or suggests the invention which here essentially applies to crude oil not yet distilled.
Le but de la présente invention est de convertir en amides, les acides organiques contenus dans un pétrole brut à acidité élevée, principalement les acides naphténiques, au cours d'un raffinage classique de ce pétrole brut en raffinerie. Les fractions distillées ainsi neutralisées, ne sont plus à l'origine de phénomènes de corrosion majeure dans les équipements traversés. D'ailleurs, ces coupes peuvent même être valorisées, ce traitement ayant pour effet de favoriser l'apparition de fonctions amides améliorant la qualités des produits commercialisés. On peut ainsi limiter l'ajout en additifs de lubrifiance dans les essences et les distillats moyens, kérosène et gazole, cette fonction de lubrifiance étant de fait déjà présente au sein de la coupe distillée.The object of the present invention is to convert into amides, the organic acids contained in a crude oil with high acidity, mainly the acids naphthenic, during a conventional refining of this crude oil in a refinery. The distilled fractions thus neutralized are no longer the cause of major corrosion phenomena in the equipment crossed. Moreover, these cuts can even be valued, this treatment having the effect of promoting the appearance of amide functions improving the quality of the products sold. It is thus possible to limit the addition of lubricating additives in gasolines and middle distillates, kerosene and diesel, this lubricating function being in fact already present within the distilled cut.
La présente invention a donc pour objet un procédé de raffinage par neutralisation de l'acidité organique des pétroles bruts à forte acidité consistant à ajouter un composé azoté au dit pétrole brut, le dit procédé étant caractérisé en ce qu'on introduit en au moins un point de l'unité de prétraitement du pétrole en amont de, ou dans l'unité de distillation atmosphérique, un composé azoté comprenant au moins trois atomes de carbone, un groupe aminé secondaire et un groupe hydroxylé. De tels composés présentent l'avantage de pouvoir réagir à froid notamment pour neutraliser les acides naphténiques en sels d'aminé, l'amidification étant réalisée par augmentation de la température du pétrole brut avant sa distillation. Les sels d'aminés résultant des acides naphténiques, demeurent dans le pétrole brut aussi bien pendant les opérations de préchauffe du pétrole brut que lors des opérations de dessalage en se transformant progressivement en amides. Ainsi, ils sont toujours présents mais sous forme amide dans le pétrole brut à son entrée dans le four de distillation atmosphérique. De ce fait, les acides naphthéniques amidifiés et les autres amides éventuellement formés à partir d'autres composés acides présents sont distillés comme les autres hydrocarbures et se retrouvent dans les différentes coupes usuellement distillées. On constate avantageusement que ces amides confèrent aux coupes distillées des propriétés inattendues de lubrifiance et d'anticorrosion. Ainsi on a ainsi constaté qu'en tête de tour il était possible de limiter voire de supprimer l'ajout d'aminés neutralisantes. En outre, les coupes de distillats moyens pour la production de gazoles présentent une acidité très réduite et un pouvoir de lubrifiant amélioré.The present invention therefore relates to a process for refining by neutralization of the organic acidity of crude oils with high acidity consisting in adding a nitrogenous compound to said crude oil, said process being characterized in that one introduces in at least one point of the petroleum pretreatment unit upstream of, or in the atmospheric distillation unit, a nitrogenous compound comprising at least three carbon atoms, a secondary amino group and a hydroxyl group. Such compounds have the advantage of being able to react cold, in particular to neutralize the naphthenic acids into amine salts, the amidification being carried out by increasing the temperature of the crude oil before its distillation. The amine salts resulting from the naphthenic acids remain in the crude oil both during the crude oil preheating operations and during the desalting operations, gradually transforming into amides. Thus, they are always present but in the amide form in the crude oil when it enters the atmospheric distillation furnace. As a result, the amidified naphthenic acids and the other amides possibly formed from other acidic compounds present are distilled like the other hydrocarbons and are found in the various cuts usually distilled. It is advantageously found that these amides give the distilled cuts unexpected properties of lubricity and anticorrosion. Thus, it was thus found that at the head of the tower it was possible to limit or even eliminate the addition of neutralizing amines. In addition, cuts of middle distillates for the production of diesel have very low acidity and improved lubricity.
Pour obtenir de tels résultats, les composés azotés utilisés sont choisis parmi les composés de formule (I) ci-après Y - OHTo obtain such results, the nitrogen compounds used are chosen from the compounds of formula (I) below: Y - OH
I H - N (I)I H - N (I)
I Z dans laquelle Y est un groupe alkyle linéaire ou ramifié comprenant de 1 à 10 atomes de carbone, éventuellement hydroxylé, et Z est choisi parmi les groupes alkyles, hydroxyalkyles et polyhydroxyalkyles (contenant jusque 6, de préférence jusque 4 hydroxy), aminés primaires, secondaires ou tertiaires et leurs dérivés hydroxylés et polyhydroxylés, les fonctions alkyles de ces groupes comprenant de 1 à 10 atomes de carbone.IZ in which Y is a linear or branched alkyl group comprising from 1 to 10 carbon atoms, optionally hydroxylated, and Z is chosen from alkyl, hydroxyalkyl and polyhydroxyalkyl groups (containing up to 6, preferably up to 4 hydroxy), primary and secondary amines or tertiary and their hydroxylated and polyhydroxylated derivatives, the alkyl functions of these groups comprising from 1 to 10 carbon atoms.
Dans un premier mode préféré de l'invention, on utilisera un composé de formule (I) dans lequel Z est un groupe choisi parmi les groupes hydroxyalkyles et polyhydroxyalkyles. Les composés de formule (I) préférés de ce premier mode sont choisis parmi les dialcanolamines du groupe constitué par la diéthanolamine, la dipropanolamine, la dibutanolamine, la N-propanol-2-éthanolamine, la N-butanol-2-éthanolamine, la N- butanol-3-éthanolamine, la N-butanol-2-propanolamine, la N-butanol-3- propanolamine, la N-propanol-2-butanolamine, la di-(méthyl1-hydroxy2)- propylamine, la diisopropanolamine et la di-(méthyl2hydroxy2)-butylamine.In a first preferred embodiment of the invention, use will be made of a compound of formula (I) in which Z is a group chosen from hydroxyalkyl and polyhydroxyalkyl groups. The preferred compounds of formula (I) of this first mode are chosen from the dialkanolamines from the group consisting of diethanolamine, dipropanolamine, dibutanolamine, N-propanol-2-ethanolamine, N-butanol-2-ethanolamine, N - butanol-3-ethanolamine, N-butanol-2-propanolamine, N-butanol-3-propanolamine, N-propanol-2-butanolamine, di- (methyl1-hydroxy2) - propylamine, diisopropanolamine and di - (méthyl2hydroxy2) -butylamine.
Pour une efficacité optimale du procédé selon l'invention, les composés préférés sont choisis parmi la diéthanolamine et la diisopropanolamine.For optimal efficiency of the process according to the invention, the preferred compounds are chosen from diethanolamine and diisopropanolamine.
Dans un deuxième mode de réalisation de l'invention, on utilisera un composé de formule (I) dans lequel Z est un groupe alkyle comprenant de 1 à 5 atomes de carbone.In a second embodiment of the invention, use will be made of a compound of formula (I) in which Z is an alkyl group comprising from 1 to 5 carbon atoms.
Les composés de formule (I) sont choisis parmi la N-méthyl-éthanolamine, la N-propyl-éthanoiamine, la N-butyléthanolamine, la N-isobutyléthanolamine, la N- pentyléthanolamine, N-méthyl-propanolamine, la N-isopentyléthanolamine, la N- propyl-propanolamine, la N-butylpropanolamine, la N-isobutylpropanolamine, la N- pentylpropanolamine, la N-isopentylpropanolamine, la N-méthyl-butanolamine, la N- propyl-butanolamine, la N-butylbutanolamine, la N-isobutyl-butanolamine, la N- pentylbutanolamine, la N-isopentylbutanolamine, la N-méthyl-pentanolamine, la N- propyl-pentanolamine, la N-butylpentanolamine, la N-isobutylpentanolamine, la N- pentylpentanolamine et la N-isopentylpentanolamine. Dans un mode optimal, on préférera comme composés de formule (I) la N-propyléthanolamine et la N- isobutyléthanolamine.The compounds of formula (I) are chosen from N-methyl-ethanolamine, N-propyl-ethanoiamine, N-butylethanolamine, N-isobutylethanolamine, N-pentylethanolamine, N-methyl-propanolamine, N-isopentylethanolamine, N-propyl-propanolamine, N-butylpropanolamine, N-isobutylpropanolamine, N-pentylpropanolamine, N-isopentylpropanolamine, N-methyl-butanolamine, N-propyl-butanolamine, N-butylbutanolamine, N-isobutyl -butanolamine, N-pentylbutanolamine, N-isopentylbutanolamine, N-methyl-pentanolamine, N-propyl-pentanolamine, N-butylpentanolamine, N-isobutylpentanolamine, N-pentylpentanolamine and N-isopentylpentanolamine. In an optimal mode, preference will be given, as compounds of formula (I), to N-propylethanolamine and N-isobutylethanolamine.
Dans un troisième mode de réalisation de l'invention, on utilisera un composé de formule (I) dans lequel Z est choisi parmi les groupes aminés primaires, secondaires et tertiaires et leurs dérivés monohydroxylés et polyhydroxylés. Les composés préférés de ce troisième mode sont choisis dans le groupe constitué par la N-Hydroxy-2-éthylhydrazine, la N-hydroxy-2-éthyiéthylènediamine, la N-hydroxy-2-éthyl-(1-3)propylènediamine, la N,N'-bis(dihydroxy-2,3-propyl)amine et la hydroxy-2-(1 ,3)propylènediamine. De préférence, la N-hydroxy-2- éthyléthylènediamine sera choisie.In a third embodiment of the invention, use will be made of a compound of formula (I) in which Z is chosen from primary, secondary and tertiary amino groups and their monohydroxylated and polyhydroxylated derivatives. The preferred compounds of this third mode are chosen from the group consisting of N-Hydroxy-2-ethylhydrazine, N-hydroxy-2-ethylethylenediamine, N-hydroxy-2-ethyl- (1-3) propylenediamine, N , N'-bis (2,3-dihydroxy-propyl) amine and hydroxy-2- (1, 3) propylenediamine. Preferably, N-hydroxy-2-ethylethylenediamine will be chosen.
Pour neutraliser puis amidifier les acides organiques du pétrole brut à raffiner, le composé de formule (I) peut être introduit avant l'unité de dessalage du pétrole brut, dans le train de préchauffe du pétrole brut dessalé, de préférence avant les échangeurs ou encore dans la tour de distillation.To neutralize and then amidify the organic acids of the crude oil to be refined, the compound of formula (I) can be introduced before the crude oil desalination unit, in the preheating train of desalted crude oil, preferably before the exchangers or else in the distillation tower.
Un autre objet de l'invention est l'application du procédé à la neutralisation des acides organiques contenus dans les pétroles bruts à acidité supérieure à 0,5 mg KOH/g. Un troisième objet de l'invention correspond aux coupes pétrolières obtenues par application du dit procédé selon le premier objet de l'invention.Another object of the invention is the application of the process for the neutralization of organic acids contained in crude oils with an acidity greater than 0.5 mg KOH / g. A third object of the invention corresponds to the petroleum fractions obtained by application of said method according to the first object of the invention.
Parmi ces coupes pétrolières, il y a les distillats moyens de température de coupe compris entre 150 et 400°CAmong these petroleum fractions, there are middle distillates with a cutting temperature between 150 and 400 ° C.
Un deuxième type de coupe correspond aux coupes dites légères de température de coupes comprises entre le point initial et 150°C et d'acidité inférieure à 0.5 mg de KOH/g.A second type of cut corresponds to the so-called light cuts of cut temperature between the initial point and 150 ° C. and of acidity less than 0.5 mg of KOH / g.
Nous décrirons maintenant l'invention sur la base d'exemples donnés ci-après visant à illustrer les caractéristiques de l'invention mais sans vouloir en limiter la portée.We will now describe the invention on the basis of examples given below aimed at illustrating the characteristics of the invention but without wishing to limit its scope.
EXEMPLE IEXAMPLE I
Le présent exemple décrit le procédé de transformation des acides organiques d'un pétrole brut par les composés azotés selon l'invention.The present example describes the process for transforming organic acids in crude petroleum with the nitrogen compounds according to the invention.
On opère avec un pétrole brut A d'acidité moyennement élevée (12,9 mmoles d'acide carboxylique/l de pétrole brut) d'une part et un pétrole brut B à acidité élevée (68,1 mmoles d'acide carboxylique/l de pétrole brut) d'autre part. On introduit dans un réacteur agité, 20 I de pétrole brut et le composé de formule (I) ici de la diéthanolamine (ou DEA). Les pétroles bruts A et B ainsi additivés sont alors analysés par infrarouge. On constate qu'il y a disparition du pic acide à 1708 cm"1 sur le s deux pétroles bruts A et B. On a donc eu transformation des acides carboxyliques en sel d'acide carboxylique. On élève alors la température de A et de B additivés à 150° pendant 30mn de manière à amidifier ces sels. Ces pétroles bruts ainsi amides sont ensuite introduits dans un pilote de distillation. Les coupes pétrolières ainsi distillées sont alors analysées par infrarouge. Ces différentes coupes sont comparées avec les coupes identiques du brut pur non traité mais distillé sur le même pilote de distillation. On constate que dans ces coupes les acides carboxyliques ont bien disparu et que des composés amides ont bien été formés.One operates with a crude oil A of medium high acidity (12.9 mmol of carboxylic acid / l of crude oil) on the one hand and a crude oil B of high acidity (68.1 mmol of carboxylic acid / l crude oil) on the other hand. Is introduced into a stirred reactor, 20 I of crude oil and the compound of formula (I) here diethanolamine (or DEA). The crude oils A and B thus added are then analyzed by infrared. It is noted that there is disappearance of the acid peak at 1708 cm −1 on the s two crude oils A and B. There has therefore been transformation of the carboxylic acids into carboxylic acid salt. The temperature of A and of B additivated at 150 ° for 30 minutes so as to amidify these salts. These crude oils thus amide are then introduced into a distillation pilot. The petroleum cuts thus distilled are then analyzed by infrared. These different cuts are compared with identical cuts of the crude pure untreated but distilled on the same distillation pilot. It can be seen that in these sections the carboxylic acids have indeed disappeared and that amide compounds have indeed been formed.
Le détail des coupes distillées est donné dans le tableau (I) ci-après. Les résultats sont donnés en mmoles d'acides carboxyliques par litre d'hydrocarbures.The details of the distilled sections are given in table (I) below. The results are given in mmoles of carboxylic acids per liter of hydrocarbons.
TABLEAU ITABLE I
On constate d'après ce tableau établi par analyse des graphes obtenus par analyse infra rouge que dans toutes les coupes obtenues sur le produit traité avant distillation, on observe une réduction notable de la teneur en acide carboxylique et donc en espèces chimiques corrosives. Ceci est particulièrement vrai pour la coupe gazole, distillée entre 230 et 350°C sur laquelle se concentre la majorité des composés naphténiques.It is noted from this table established by analysis of the graphs obtained by infrared analysis that in all the cuts obtained on the product treated before distillation, there is a significant reduction in the content of carboxylic acid and therefore in corrosive chemical species. This is particularly true for the diesel cut, distilled between 230 and 350 ° C on which the majority of naphthenic compounds are concentrated.
EXEMPLE IIEXAMPLE II
Le présent exemple a pour but de décrire les avantages liés au procédé en ce qui concerne l'amélioration de la lubrifiance des coupes distillats moyens et l'effet anticorrosion des amides formés dans les coupes légères de distillation.The purpose of the present example is to describe the advantages linked to the process with regard to the improvement of the lubricity of middle distillate cuts and the anticorrosion effect of the amides formed in light distillation cuts.
On reprend donc les coupes 230-350°C de l'exemple I avec et sans amidification avant distillation et on mesure sur chacune d'elles la lubrifiance par la méthode dite HFRR (High Frequency Reciprocating Ring), selon la norme EC12156- 1. On l'exprime en diamètre d'usure (WSR: Wear Scare Diameter) en μm. Une lubrifiance correcte conduit à des valeurs de diamètre d'usure inférieures à 460μm. Plus cette valeur est faible, meilleure est la lubrifiance.The 230-350 ° C sections of Example I are therefore taken up again with and without amidation before distillation and the lubricity is measured on each of them by the method known as HFRR (High Frequency Reciprocating Ring), according to standard EC12156-1. It is expressed in wear diameter (WSR: Wear Scare Diameter) in μm. Correct lubrication leads to wear diameter values of less than 460 μm. The lower this value, the better the lubricity.
Les résultats sont donnés dans le tableau II ci-après. TABLEAUThe results are given in Table II below. BOARD
Les résultats montrent que, bien que les acides carboxyliques et en particulier les acides naphténiques aient un rôle d'améliorant de la lubrifiance bien connu, la disparitions de ces acides par amidification n'a pas d'effet néfaste sur la lubrifiance. L'effet des acides comme améliorant de lubrifiance de la coupe gazole (230-350°C), en particulier celle des pétroles bruts à forte acidité organique (B), a été remplacé par l'effet de l'amide correspondant.The results show that, although the carboxylic acids and in particular the naphthenic acids have a well-known role in improving lubricity, the disappearance of these acids by amidification has no harmful effect on the lubricity. The effect of acids as a lubricant improver in the diesel cut (230-350 ° C), in particular that of crude oils with high organic acidity (B), has been replaced by the effect of the corresponding amide.
EXEMPLE IIIEXAMPLE III
Le présent exemple vise à montrer le caractère progressif de la réaction des alcanolamines en particulier de la diéthanolamine (DEA) sur le pétrole brut B d'acidité correspondant un TAN de 4,47 soit 68 mmole/l d'acidité mesurée. Pour le suivi de la réaction, on introduit dans un ballon de 500 ml 434 g de pétrole brut B et 13 ml de DEA diluée à 40% en poids dans de l'eau. On procède à l'addition progressive de DEA pendant 50 minutes tout en agitant au moyen d'un agitateur magnétique classique le mélange.The present example aims to show the progressive nature of the reaction of the alkanolamines in particular of diethanolamine (DEA) on crude oil B with an acidity corresponding to a TAN of 4.47 or 68 mmol / l of acidity measured. To monitor the reaction, 434 g of crude oil B and 13 ml of DEA diluted to 40% by weight in water are introduced into a 500-ml flask. The DEA is gradually added over 50 minutes while stirring the mixture using a conventional magnetic stirrer.
Cet ajout est suivi par un chauffage du pétrole brut B jusqu'à 100°, puis jusqu'à 150°C pendant 30 minutes. La température est ensuite stabilisée à 180°C au bout de 2 heures.This addition is followed by heating the crude oil B to 100 °, then to 150 ° C for 30 minutes. The temperature is then stabilized at 180 ° C after 2 hours.
On suit la réaction au sein du pétrole brut au cours de l'addition de DEA par spectromètrie IRFT au moyen d'une canne de mesure plongée dans le pétrole brut B faisant partie du spectromètre REACT IR commercialisé par la société METTLER.The reaction is followed within the crude oil during the addition of DEA by IRFT spectrometry using a measuring rod immersed in crude oil B forming part of the REACT IR spectrometer sold by the company METTLER.
On mesure périodiquement au cours de cette réaction les spectres infrarouges du produit contenu dans le ballon.During this reaction, the infrared spectra of the product contained in the flask are measured periodically.
Les figures 1 et 2 donnent une représentation de l'évolution des spectres infrarouges au cours de l'addition de DEA et au cours du chauffage en fonction du temps. La figure 1 présente, en trois dimensions, la disparition des dérivés acides (bande centrée sur la longueur d'onde 1710 cm"1), l'apparition de sels d'aminés (bande centrée sur 1560 cm"1) et l'apparition des amides (bande centrée sur 1650 cm"1).Figures 1 and 2 give a representation of the evolution of the infrared spectra during the addition of DEA and during heating as a function of time. Figure 1 shows, in three dimensions, the disappearance of the acid derivatives (band centered on the wavelength 1710 cm "1 ), the appearance of amine salts (band centered on 1560 cm " 1 ) and the appearance amides (strip centered on 1650 cm "1 ).
La figure 2 représente, en deux dimensions, en fonction du temps, la formation d'amide (bande centrée sur 650 cm"1) après ajout de DEA et le maintien du pétrole brut B une heure à 140°C. On note également la formation d'esters en faible quantité liée à la présence d'eau amenée par l'addition de DEA (bande centrée sur 1740 cm"1). FIG. 2 represents, in two dimensions, as a function of time, the formation of amide (band centered on 650 cm −1 ) after addition of DEA and the maintenance of crude oil B for one hour at 140 ° C. The formation of esters in small quantities linked to the presence of water supplied by the addition of DEA (band centered on 1740 cm −1 ).

Claims

REVENDICATIONS
1. Procédé de raffinage par neutralisation de l'acidité organique des pétroles bruts à forte acidité consistant à ajouter un composé azoté au dit pétrole brut, le dit procédé étant caractérisé en ce qu'on introduit en au moins un point de l'unité de prétraitement de pétrole brut en amont de ou dans l'unité de distillation atmosphérique un composé azoté comprenant au moins trois atomes de carbone, un groupe aminé secondaire et un groupe hydroxyle.1. Method for refining by neutralization of the organic acidity of crude oils with high acidity consisting in adding a nitrogenous compound to said crude oil, said method being characterized in that one introduces at at least one point of the unit of pretreatment of crude oil upstream from or in the atmospheric distillation unit a nitrogenous compound comprising at least three carbon atoms, a secondary amino group and a hydroxyl group.
2. Procédé selon la revendication 1 caractérisé en ce que les composés azotés utilisés sont choisis parmi les composés de formule (I) ci-après Y - OH2. Method according to claim 1 characterized in that the nitrogen compounds used are chosen from the compounds of formula (I) below Y - OH
H - N )H - N)
Z dans laquelle Y est un groupe alkyle linéaire ou ramifié comprenant de 1 à 10 atomes de carbone, éventuellement hydroxyle, et Z est choisi parmi les groupes alkyles, hydroxyalkyles et polyhydroxyalkyles, aminés primaires, secondaires ou tertiaires et leurs dérivés hydroxylés et polyhydroxylés, les fonctions alkyles de ces groupes comprenant de 1 à 10 atomes de carbone.Z in which Y is a linear or branched alkyl group comprising from 1 to 10 carbon atoms, optionally hydroxyl, and Z is chosen from alkyl, hydroxyalkyl and polyhydroxyalkyl groups, primary, secondary or tertiary amines and their hydroxylated and polyhydroxylated derivatives, the alkyl functions of these groups comprising from 1 to 10 carbon atoms.
3. Procédé selon les revendications 1 et 2 caractérisé en ce que dans le composé de formule (I), lequel Z est un groupe choisi parmi les groupes hydroxyalkyles et polyhydroxyalkyles.3. Method according to claims 1 and 2 characterized in that in the compound of formula (I), which Z is a group chosen from hydroxyalkyl and polyhydroxyalkyl groups.
4. Procédé selon les revendications 1 à 3 caractérisé en ce que le composé de formule (I) est choisi dans le groupe constitué par la diéthanolamine, la dipropanolamine, la dibutanolamine, la N-propanol-2-éthanolamine, la N- butanol-2-éthanolamine, la N-butanol-3-éthanolamine, la N-butanol-2- propanolamine, la N-butanol-3-propanolamine, la N-propanol-2-butanolamine, la di-(méthyl1-hydroxy2)-propylamine, le diisopropanolamine et la di- (méthyl2hydroxy2)-butylamine.4. Method according to claims 1 to 3 characterized in that the compound of formula (I) is chosen from the group consisting of diethanolamine, dipropanolamine, dibutanolamine, N-propanol-2-ethanolamine, N-butanol- 2-ethanolamine, N-butanol-3-ethanolamine, N-butanol-2-propanolamine, N-butanol-3-propanolamine, N-propanol-2-butanolamine, di- (methyl1-hydroxy2) -propylamine , diisopropanolamine and di- (methyl2hydroxy2) -butylamine.
5. Procédé selon la revendication 4 caractérisé en ce que le composé de formule (I) est choisi parmi la diéthanolamine et la diisopropanolamine. 5. Method according to claim 4 characterized in that the compound of formula (I) is chosen from diethanolamine and diisopropanolamine.
6. Procédé selon les revendications 1 et 2 caractérisé en ce que dans le composé de formule (I), Z est un groupe alkyle comprenant de 1 à 5 atomes de carbone.6. Method according to claims 1 and 2 characterized in that in the compound of formula (I), Z is an alkyl group comprising from 1 to 5 carbon atoms.
7. Procédé selon la revendication 6 caractérisé en ce que le composé de formule (I) est choisi parmi la N-méthyl-éthanolamine, la N-propyl-éthanolamine, la N- butyléthanolamine, la N-isobutyléthanolamine, la N- pentyléthanolamine, N- méthyl-propanolamine, la N-isopentyléthanolamine, la N-propyl-propanolamine, la N-butylpropanolamine, la N-isobutylpropanolamine, la N- pentylpropanolamine, la N-isopentylpropanolamine, la N-méthyl-butanolamine, la N-propyl-butanolamine, la N-butylbutanolamine, la N-isobutyl-butanolamine, la N- pentylbutanolamine, la N-isopentylbutanolamine, la N-méthyl- pentanolamine, la N-propyl-pentanolamine, la N-butylpentanolamine, la N- isobutylpentanolamine, la N- pentylpentanolamine et la N- isopentylpentanolamine.7. Method according to claim 6 characterized in that the compound of formula (I) is chosen from N-methyl-ethanolamine, N-propyl-ethanolamine, N-butylethanolamine, N-isobutylethanolamine, N-pentylethanolamine, N-methyl-propanolamine, N-isopentylethanolamine, N-propyl-propanolamine, N-butylpropanolamine, N-isobutylpropanolamine, N-pentylpropanolamine, N-isopentylpropanolamine, N-methyl-butanolamine, N-propyl- butanolamine, N-butylbutanolamine, N-isobutyl-butanolamine, N-pentylbutanolamine, N-isopentylbutanolamine, N-methyl-pentanolamine, N-propyl-pentanolamine, N-butylpentanolamine, N-isobutylpentanolamine, N - pentylpentanolamine and N-isopentylpentanolamine.
8. Procédé selon les revendications 6 et 7, caractérisé en ce que le composé de formule (I) est choisi parmi la N-propyléthanolamine et la N- isobutyléthanolamine.8. Method according to claims 6 and 7, characterized in that the compound of formula (I) is chosen from N-propylethanolamine and N-isobutylethanolamine.
9. Procédé selon les revendications 1 et 2 caractérisé en ce que dans le composé de formule (I), Z est choisi parmi les groupes aminés primaires, secondaires et tertiaires et leurs dérivés monohydroxylés et polyhydroxylés.9. Method according to claims 1 and 2 characterized in that in the compound of formula (I), Z is chosen from primary, secondary and tertiary amino groups and their monohydroxylated and polyhydroxylated derivatives.
10. Procédé selon la revendication 9 caractérisé en ce que le composé de formule (I) est choisi dans le groupe constitué par la N-Hydroxy-2-éthylhydrazine, la N- hydroxy-2-éthyléthylènediamine, la N-hydroxy-2-éthyl-(1 -3)propylènediamine, la N,N'-bis(dihydroxy-2,3-propyl)amine et la hydroxy-2-(1 ,3)propylènediamine.10. Method according to claim 9 characterized in that the compound of formula (I) is chosen from the group consisting of N-Hydroxy-2-ethylhydrazine, N-hydroxy-2-ethylethylenediamine, N-hydroxy-2- ethyl- (1 -3) propylenediamine, N, N'-bis (2,3-dihydroxy-propyl) amine and hydroxy-2- (1, 3) propylenediamine.
11. Procédé selon les revendications 9 et 10 caractérisé en ce que le composé de formule (I) est la N-hydroxy-2-éthyléthylènediamine.11. Method according to claims 9 and 10 characterized in that the compound of formula (I) is N-hydroxy-2-ethylethylenediamine.
12. Procédé selon les revendications 1 à 11 caractérisé en ce que le composé azoté est introduit avant l'unité de dessalage du pétrole brut, dans le train de préchauffe du pétrole brut dessalé, de préférence avant les échangeurs ou encore dans la tour de distillation.12. Method according to claims 1 to 11 characterized in that the nitrogenous compound is introduced before the crude oil desalination unit, in the preheating train of desalted crude oil, preferably before the exchangers or also in the distillation tower .
13. Procédé selon l'une des revendications 1 à 12 dans lesquels les pétroles bruts présentent une acidité organique et acidité totale supérieure à 0,5 mg KOH/g. 13. Method according to one of claims 1 to 12 wherein the crude oils have an organic acidity and total acidity greater than 0.5 mg KOH / g.
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CA2452327C (en) 2010-06-29
OA12611A (en) 2006-06-09
FR2825369A1 (en) 2002-12-06
US20040134838A1 (en) 2004-07-15

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