EP1205531A1 - Process for hydrotreatment of hydrocarbon mixtures rich in olefines and aromatics - Google Patents

Process for hydrotreatment of hydrocarbon mixtures rich in olefines and aromatics Download PDF

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Publication number
EP1205531A1
EP1205531A1 EP00203887A EP00203887A EP1205531A1 EP 1205531 A1 EP1205531 A1 EP 1205531A1 EP 00203887 A EP00203887 A EP 00203887A EP 00203887 A EP00203887 A EP 00203887A EP 1205531 A1 EP1205531 A1 EP 1205531A1
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EP
European Patent Office
Prior art keywords
process according
ammonia
chosen
compounds
hydrotreatment
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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
EP00203887A
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German (de)
French (fr)
Inventor
Catherine Olivier
Walter Vermeiren
Jean-Pierre Dath
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Total Research and Technology Feluy SA
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Atofina Research SA
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Publication date
Application filed by Atofina Research SA filed Critical Atofina Research SA
Priority to EP00203887A priority Critical patent/EP1205531A1/en
Priority to US10/416,058 priority patent/US7399402B2/en
Priority to KR1020037006246A priority patent/KR100591577B1/en
Priority to AU2002219087A priority patent/AU2002219087A1/en
Priority to ES01993659T priority patent/ES2363494T3/en
Priority to PCT/EP2001/012989 priority patent/WO2002038701A1/en
Priority to JP2002542022A priority patent/JP4900885B2/en
Priority to EP01993659A priority patent/EP1334167B1/en
Priority to AT01993659T priority patent/ATE509997T1/en
Publication of EP1205531A1 publication Critical patent/EP1205531A1/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Withdrawn legal-status Critical Current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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/32—Selective hydrogenation of the diolefin or acetylene 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4081—Recycling aspects
    • 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 hydrotreating a mixture of hydrocarbon compounds comprising from four to eight carbon atoms, rich in olefins and monoaromatic compounds. It concerns more particularly the hydrotreatment of the sections resulting from the distillation of crude oils, steam cracking, catalytic reforming, cracking catalytic, coking or any process producing such cuts and cuts from the processing of coal such as coal essences.
  • the present application therefore relates to a process which neither requires nor pretreatment of the catalyst, or introduction of nitrogenous gaseous compounds into hydrogenation gas. It aims at a simple process which can be easily implemented whatever the hydrotreatment unit, with a little catalyst expensive compared to catalysts containing noble metals such as platinum and palladium, which can adapt to fillers whose composition can vary in concentration of olefins and monoaromatic compounds and which allows good desulfurization of the feed.
  • olefins is meant here the monoolefinic and diolefinic compounds generally present in the charges sent for hydrotreatment.
  • the present invention therefore relates to a hydrotreatment process a mixture of hydrocarbon compounds from C4 to C8, rich in olefins and monoaromatic compounds, by hydrogenation in the presence of a catalyst solid, characterized in that an ammonia precursor is introduced into the charge of hydrocarbon compounds and that the catalyst comprises at least a transition metal supported on at least one refractory oxide.
  • Transition metal means any transition metal except so-called noble metals, in particular platinum and palladium.
  • One of the advantages of the process is linked to the introduction of a precursor of ammonia in the charge which makes it possible to release, during the reaction, from gaseous ammonia which is present during the selective hydrogenation reaction olefins and which can be recovered and recycled with unused hydrogen.
  • this method makes it possible to control precisely the amount of ammonia released during the reaction hydrotreating. In addition, it helps to limit unwanted reactions oligomerization while maintaining excellent catalyst activity for the desired reactions for selective hydrogenation of olefins and charge desulfurization.
  • the Applicant has found that from a on the other hand, the oligomerization of aromatic compounds results from the presence of acid sites on the catalyst, these sites being of variable acid forces.
  • the efficiency of the hydrotreatment reaction depends on the electrodeficiency of the catalytic support which itself is correlated with its acidity.
  • injected not more than 1000 ppm by weight of molar equivalent nitrogen of precursor of ammonia in the feed is injected not more than 1000 ppm by weight of molar equivalent nitrogen of precursor of ammonia in the feed.
  • 5 to 1000 ppm by weight of nitrogen molar equivalent will be injected nitrogen precursor, and preferably from 10 to 200 ppm.
  • the ammonia precursors are chosen from nitrogen compounds capable of releasing ammonia gas under hydrotreatment conditions.
  • the ammonia precursor is chosen from linear and branched amines, polyamines, imines, and urea and its derivatives.
  • the amines and polyamines are chosen from the group consisting of mono, di and trialkylamines comprising from 1 to 10 carbon atoms by alkyl group, the alkyl groups being linear or cyclic, and polyalkylamines comprising from 1 to 5 atoms nitrogen, each alkyl group comprising from 1 to 6 carbon atoms in linear or branched form.
  • Preferred amines and polyamines are selected from methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, cyclohexylamine, cycloheptylamine, dimethylamine, diethylamine dipropylamine, dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, methylenediamine, ethylenediamine, propylenediamine, butylenediamine, dimethylenetriamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine and tetrapropylenepentamine, cyclohexylamine, triethylamine and ethylenediamine being preferred.
  • the catalyst necessary for the process according to the invention consists of at least minus one metal chosen from the group consisting of nickel, cobalt, molybdenum, vanadium and tungsten; nickel alone and combinations nickel / molybdenum, cobalt / molybdenum and nickel / tungsten are preferred.
  • This or these metals are supported on at least one refractory oxide chosen from alumina, silica, silicoalumines, aluminophosphates, zirconia, magnesia and the oxides of titanium, rutile and anatase, these oxides occurring in amorphous or crystalline form.
  • the operation is carried out at a temperature between 50 and 400 ° C., under a pressure between 10 6 Pa and 10 7 Pa, preferably between 3 ⁇ 10 6 Pa and 6 ⁇ 10 6 Pa, and a hvv varying from 0.5 to 10h -1 .
  • ammonia gaseous excess formed can be recycled into the recycle gas rich in hydrogen. This has the advantage of limiting the amount of precursor of ammonia injected into the load.
  • This example describes the conditions under which the invention is achieved by presenting the gain brought by the introduction of precursor of ammonia in an industrial load to be hydrotreated and this for different ammonia precursors and for different concentrations thereof.
  • the benzene content was measured using the UOP 744-86 method referenced in the "Laboratory test methods for petroleum and its products", published by UOP Process Division, (UOP Inc. 20 UOP Plaza-Algonquin Mt Prospect Roads-Des Plains-Illinois 60016).
  • the olefin content is determined by measuring the number of bromine in application of standard ASTM D1159, and the sulfur content by method ASTM D2622.
  • Three ammonia precursors were used on a hydrotreatment pilot unit for 100 ml of catalyst, at a temperature of 200 ° C., a pressure of 26.5 ⁇ 10 5 Pa, operating with an H2 / hydrocarbon ratio of 230NI / l, wh of the charge being 1.6h -1 .
  • These precursors are triethyleneamine or TEA, cyclohexylamine or CHA and ethylenediamine or EDA.
  • the present example aims to emphasize the effectiveness of the process whatever either the relative concentrations of the load in olefins and in compounds monoaromatic.
  • cyclohexylamine or CHA is used as ammonia precursor.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Hydro treatment of an olefin- and mono aromatics-rich hydrocarbon feed comprises: (1) adding an ammonia precursor to the feed; and (2) contacting it with hydrogen in the presence of a transition metal catalyst on a refractory oxide support. Hydro treatment of an olefin- and mono aromatics-rich 1-4C hydrocarbon feed comprises: (1) adding an ammonia precursor to the feed; and (2) contacting it with hydrogen in the presence of a transition metal catalyst on a refractory oxide support.

Description

La présente invention concerne un procédé d'hydrotraitement d'un mélange de composés hydrocarbonés comprenant de quatre à huit atomes de carbone, riche en oléfines et en composés monoaromatiques. Il concerne plus particulièrement l'hydrotraitement des coupes résultant de la distillation de pétroles bruts, du vapocraquage, du réformage catalytique, du craquage catalytique, du cokage ou de tous procédés produisant de telles coupes et les coupes issues du traitement de la houille comme les essences de houille.The present invention relates to a process for hydrotreating a mixture of hydrocarbon compounds comprising from four to eight carbon atoms, rich in olefins and monoaromatic compounds. It concerns more particularly the hydrotreatment of the sections resulting from the distillation of crude oils, steam cracking, catalytic reforming, cracking catalytic, coking or any process producing such cuts and cuts from the processing of coal such as coal essences.

Il est bien connu d'hydrotraiter toutes les coupes issues de la distillation des pétroles bruts en présence d'hydrogène et d'un catalyseur constitué de métaux de transition supportés sur des oxydes réfractaires. Il est beaucoup moins évident d'hydrotraiter dans ces conditions des mélanges hydrocarbonés contenant de fortes quantités d'oléfines de composés de C4 à C8 et contenant de fortes proportions de composés monoaromatiques tels que le benzène, le toluène et le xylène. Au cours de l'hydrotraitement, il y a hydrogénation totale ou partielle des oléfines et des dioléfines et oligomérisation des composés monoaromatiques formant des composés en C12 et plus. Or lorsque la charge hydrogènée et désulfurée subit ultérieurement le traitement classique de distillation extractive par solvant afin d'extraire les composés monoaromatiques contenus, certains oligomères présents, formés lors de l'hydrotraitement ne peuvent être éliminés du solvant car leur point d'ébullition est trop proche de celui du solvant. En conséquence, ces oligomères s'accumulent dans le solvant d'extraction et il devient périodiquement nécessaire d'arrêter la distillation pour changer le solvant afin de l'épurer. Le coût de cette opération n'est pas négligeable en ce qu'il comprend le coût d'épuration du solvant, le coût d'achat éventuel du nouveau solvant propre, le coût opératoire lié à l'interruption de l'unité pour changer de solvant et le coût correspondant à la perte en composés monoaromatiques qui ne peuvent être vendus. It is well known to hydrotreat all cuts from distillation crude oils in the presence of hydrogen and a catalyst consisting of transition metals supported on refractory oxides. He is a lot less obvious to hydrotreat hydrocarbon mixtures under these conditions containing large amounts of olefins from C4 to C8 and containing high proportions of monoaromatic compounds such as benzene, toluene and xylene. During hydrotreatment, there is total hydrogenation or partial olefins and diolefins and oligomerization of compounds monoaromatics forming C12 and higher compounds. Now when the charge hydrogenated and desulfurized subsequently undergoes the conventional treatment of extractive solvent distillation to extract monoaromatic compounds contained, certain oligomers present, formed during hydrotreatment do not can be removed from the solvent because their boiling point is too close to that of the solvent. As a result, these oligomers accumulate in the extraction solvent and it becomes periodically necessary to stop the distillation to change the solvent in order to purify it. The cost of this operation is not negligible in that it includes the cost of cleaning the solvent, the possible purchase cost of the new clean solvent, the operating cost linked to the interruption of the unit to change the solvent and the cost corresponding to the loss of monoaromatic compounds which cannot be sold.

Ces problèmes d'hydrogénation sélective des composés oléfiniques en présence de fortes quantités de composés aromatiques ont été résolus dans le brevet français 2.376.100. Ce brevet propose de prétraiter le catalyseur supporté constitué d'au moins un métal noble sur alumine, comme le ruthénium, le rhodium, le platine et/ou le palladium par un courant d'ammoniac gazeux et éventuellement en continuant le traitement par injection de cet ammoniac gazeux dans le réacteur durant l'hydrogénation elle-même. Un tel traitement présente l'inconvénient majeur de devoir prétraiter le catalyseur in-situ dans une atmosphère contrôlée d'ammoniac seul ou en mélange avec un autre gaz inerte tel que l'azote, donc sous pression. Une telle situation est peu appréciée en milieu industriel car elle impose des contraintes de sécurité. En outre, par cette voie, il est difficile de contrôler la quantité d'ammoniac mis en contact avec le catalyseur : une quantité trop importante d'ammoniac conduit à une désactivation du catalyseur, y compris pour les réactions escomptées.These problems of selective hydrogenation of olefinic compounds into presence of large amounts of aromatics have been resolved in the French patent 2,376,100. This patent proposes to pretreat the catalyst supported consisting of at least one noble metal on alumina, such as ruthenium, rhodium, platinum and / or palladium by a stream of ammonia gaseous and possibly continuing the injection treatment of this gaseous ammonia in the reactor during the hydrogenation itself. Such treatment has the major drawback of having to pretreat the catalyst in situ in a controlled atmosphere of ammonia alone or mixed with a other inert gas such as nitrogen, therefore under pressure. Such a situation is little appreciated in an industrial environment because it imposes security constraints. In moreover, by this route, it is difficult to control the amount of ammonia put in contact with the catalyst: too much ammonia leads to deactivation of the catalyst, including for the expected reactions.

La présente demande vise donc un procédé qui ne nécessite ni prétraitement du catalyseur, ni d'introduction de composés azotés gazeux dans le gaz d'hydrogénation. Elle vise un procédé simple qui peut être facilement mis en oeuvre quelle que soit l'unité d'hydrotraitement, avec un catalyseur peu onéreux comparé aux catalyseurs contenant des métaux nobles tels que le platine et le palladium, qui peut s'adapter aux charges dont la composition peut varier en concentration en oléfines et en composés monoaromatiques et qui permet une bonne désulfuration de la charge.The present application therefore relates to a process which neither requires nor pretreatment of the catalyst, or introduction of nitrogenous gaseous compounds into hydrogenation gas. It aims at a simple process which can be easily implemented whatever the hydrotreatment unit, with a little catalyst expensive compared to catalysts containing noble metals such as platinum and palladium, which can adapt to fillers whose composition can vary in concentration of olefins and monoaromatic compounds and which allows good desulfurization of the feed.

On entend ici par oléfines les composés monooléfiniques et dioléfiniques généralement présents dans les charges envoyées pour hydrotraitement.By olefins is meant here the monoolefinic and diolefinic compounds generally present in the charges sent for hydrotreatment.

La présente invention a donc pour objet un procédé d'hydrotraitement d'un mélange de composés hydrocarbonés de C4 à C8, riche en oléfines et en composés monoaromatiques, par hydrogénation en présence d'un catalyseur solide caractérisé en ce qu'on introduit un précurseur d'ammoniac dans la charge de composés hydrocarbonés et que le catalyseur comprend au moins un métal de transition supporté sur au moins un oxyde réfractaire. The present invention therefore relates to a hydrotreatment process a mixture of hydrocarbon compounds from C4 to C8, rich in olefins and monoaromatic compounds, by hydrogenation in the presence of a catalyst solid, characterized in that an ammonia precursor is introduced into the charge of hydrocarbon compounds and that the catalyst comprises at least a transition metal supported on at least one refractory oxide.

On entend par métal de transition tout métal de transition à l'exception des métaux dits nobles, notamment le platine et le palladium.Transition metal means any transition metal except so-called noble metals, in particular platinum and palladium.

Un des avantages du procédé est lié à l'introduction d'un précurseur d'ammoniac dans la charge qui permet de libérer au cours de la réaction, de l'ammoniac gazeux qui est présent lors de la réaction d'hydrogénation sélective des oléfines et qui peut être récupéré et recyclé avec l'hydrogène inutilisé. Parmi les autres avantages liés à l'invention, ce procédé permet de contrôler avec précision la quantité d'ammoniac libéré au cours de la réaction d'hydrotraitement. En outre, il permet de limiter les réactions non souhaitées d'oligomérisation tout en maintenant une excellente activité du catalyseur pour les réactions souhaitées d'hydrogénation sélective des oléfines et de désulfuration de la charge.One of the advantages of the process is linked to the introduction of a precursor of ammonia in the charge which makes it possible to release, during the reaction, from gaseous ammonia which is present during the selective hydrogenation reaction olefins and which can be recovered and recycled with unused hydrogen. Among the other advantages linked to the invention, this method makes it possible to control precisely the amount of ammonia released during the reaction hydrotreating. In addition, it helps to limit unwanted reactions oligomerization while maintaining excellent catalyst activity for the desired reactions for selective hydrogenation of olefins and charge desulfurization.

Sans être liée par une théorie, la Demanderesse a constaté que d'une part, l'oligomérisation des composés aromatiques résulte de la présence de sites acides sur le catalyseur, ces sites étant de forces acides variables. D'autre part, l'efficacité de la réaction d'hydrotraitement dépend de l'électrodéficience du support catalytique qui elle-même est corrélée avec son acidité.Without being bound by a theory, the Applicant has found that from a On the other hand, the oligomerization of aromatic compounds results from the presence of acid sites on the catalyst, these sites being of variable acid forces. On the other hand, the efficiency of the hydrotreatment reaction depends on the electrodeficiency of the catalytic support which itself is correlated with its acidity.

Il s'agit donc de bloquer sélectivement les sites responsables des réactions d'oligomérisation des composés aromatiques, sites dont la force acide est telle qu'ils restent saturés d'ammoniac dans les conditions retenues de température et pression pour la réaction d'hydrotraitement dans le cadre de la présente invention. Malgré tout, dans ces conditions, il reste suffisamment de sites électrodéficients pour maintenir une bonne activité du procédé d'hydrotraitement.It is therefore a matter of selectively blocking the sites responsible for oligomerization reactions of aromatic compounds, sites whose strength acid is such that they remain saturated with ammonia under the conditions selected of temperature and pressure for the hydrotreatment reaction in the context of the present invention. However, under these conditions, there is still enough electrodeficient sites to maintain good process activity hydrotreating.

De façon plus précise, dans le cadre de la présente invention, on injecte au plus 1000 ppm en poids d'équivalent molaire azote de précurseur d'ammoniac dans la charge. Pour une efficacité optimale du procédé selon l'invention, on injectera de 5 à 1000 ppm en poids d'équivalent molaire azote de précurseur d'azote, et de préférence de 10 à 200 ppm.More specifically, in the context of the present invention, injected not more than 1000 ppm by weight of molar equivalent nitrogen of precursor of ammonia in the feed. For optimal process efficiency according to the invention, 5 to 1000 ppm by weight of nitrogen molar equivalent will be injected nitrogen precursor, and preferably from 10 to 200 ppm.

Pour la mise en oeuvre du procédé, les précurseurs d'ammoniac sont choisis parmi les composés azotés susceptibles de libérer de l'ammoniac gazeux dans les conditions de l'hydrotraitement.For the implementation of the process, the ammonia precursors are chosen from nitrogen compounds capable of releasing ammonia gas under hydrotreatment conditions.

Dans un mode préféré de l'invention, le précurseur d'ammoniac est choisi parmi les amines linéaires et branchées, les polyamines, les imines, et l'urée et ses dérivés. Les amines et les polyamines sont choisies dans le groupe constitué par les mono, di et trialkylamines comprenant de 1 à 10 atomes de carbone par groupement alkyles, les groupements alkyles étant linéaires ou cycliques, et les polyalkylamines comprenant de 1 à 5 atomes d'azote, chaque groupement alkylés comprenant de 1 à 6 atomes de carbone sous forme linéaire ou ramifiée. Les amines et les polyamines préférées sont choisies parmi la méthylamine, l'éthylamine, la propylamine, la butylamine, la pentylamine, l'hexylamine, l'heptylamine, la cyclohexylamine, la cycloheptylamine, la diméthylamine, la diéthylamine la dipropylamine, la dibutylamine, la triméthylamine, la triéthylamine, la tripropylamine, la tributylamine, la méthylènediamine, l'éthylènediamine, la propylènediamine, la butylènediamine, la diméthylènetriamine, la diéthylènetriamine, la dipropylènetriamine, la triéthylènetétramine, la tripropylènetétramine, la tétraéthylènepentamine et la tétrapropylènepentamine, la cyclohexylamine, la triéthylamine et l'éthylènediamine étant préférées.In a preferred embodiment of the invention, the ammonia precursor is chosen from linear and branched amines, polyamines, imines, and urea and its derivatives. The amines and polyamines are chosen from the group consisting of mono, di and trialkylamines comprising from 1 to 10 carbon atoms by alkyl group, the alkyl groups being linear or cyclic, and polyalkylamines comprising from 1 to 5 atoms nitrogen, each alkyl group comprising from 1 to 6 carbon atoms in linear or branched form. Preferred amines and polyamines are selected from methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, cyclohexylamine, cycloheptylamine, dimethylamine, diethylamine dipropylamine, dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, methylenediamine, ethylenediamine, propylenediamine, butylenediamine, dimethylenetriamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine and tetrapropylenepentamine, cyclohexylamine, triethylamine and ethylenediamine being preferred.

Le catalyseur nécessaire au procédé selon l'invention est constitué d'au moins un métal choisi dans le groupe constitué par le nickel, le cobalt, le molybdène, le vanadium et le tungstène ; le nickel seul et les combinaisons nickel/molybdène, cobalt/molybdène et nickel/tungstène sont préférés. Ce ou ces métaux sont supportés sur au moins un oxyde réfractaire choisi parmi l'alumine, la silice, les silicoalumines, les aluminophosphates, la zircone, la magnésie et les oxydes de titane, rutile et anatase, ces oxydes se présentant sous forme amorphe ou cristalline. The catalyst necessary for the process according to the invention consists of at least minus one metal chosen from the group consisting of nickel, cobalt, molybdenum, vanadium and tungsten; nickel alone and combinations nickel / molybdenum, cobalt / molybdenum and nickel / tungsten are preferred. This or these metals are supported on at least one refractory oxide chosen from alumina, silica, silicoalumines, aluminophosphates, zirconia, magnesia and the oxides of titanium, rutile and anatase, these oxides occurring in amorphous or crystalline form.

Pour une efficacité optimale de la réaction d'hydrotraitement, on opère à une température comprise entre 50 et 400°C, sous une pression comprise entre 106 Pa et 107Pa, de préférence entre 3x106 Pa et 6x106 Pa, et une vvh variant de 0,5 à 10h-1.For optimal efficiency of the hydrotreatment reaction, the operation is carried out at a temperature between 50 and 400 ° C., under a pressure between 10 6 Pa and 10 7 Pa, preferably between 3 × 10 6 Pa and 6 × 10 6 Pa, and a hvv varying from 0.5 to 10h -1 .

Dans un mode préféré du procédé d'hydrotraitement, l'ammoniac gazeux formé excédentaire peut être recyclé dans le gaz de recycle riche en hydrogène. Ceci présente l'avantage de limiter la quantité de précurseur d'ammoniac injectée dans la charge.In a preferred mode of the hydrotreatment process, ammonia gaseous excess formed can be recycled into the recycle gas rich in hydrogen. This has the advantage of limiting the amount of precursor of ammonia injected into the load.

Les exemples ci-après sont donnés pour illustrer l'invention sans vouloir en limiter la portée.The examples below are given to illustrate the invention without wishing to limit its scope.

EXEMPLE IEXAMPLE I

Le présent exemple décrit les conditions dans lesquelles l'invention est réalisée en présentant le gain apporté par l'introduction de précurseur d'ammoniac dans une charge industrielle à hydrotraiter et cela pour différents précurseurs d'ammoniac et pour différentes concentrations de ceux-ci.This example describes the conditions under which the invention is achieved by presenting the gain brought by the introduction of precursor of ammonia in an industrial load to be hydrotreated and this for different ammonia precursors and for different concentrations thereof.

La charge à hydrotraiter est un mélange à 21 % en poids d'une coupe C6 de réformage et 79% en poids d'une coupe C6 d'essence de pyrolyse. Elle contient :

  • 57% en poids de benzène
  • 12% en poids d'oléfines
  • 12 ppm en poids de soufre total
The feed to be hydrotreated is a mixture at 21% by weight of a C6 reforming cut and 79% by weight of a C6 cut of pyrolysis gasoline. It contains :
  • 57% by weight of benzene
  • 12% by weight of olefins
  • 12 ppm by weight of total sulfur

La teneur en benzène a été mesurée en application de la méthode UOP 744-86 référencée dans le « Laboratory test methods for petroleum and its products », publié par UOP Process Division, (UOP Inc. 20 UOP Plaza-Algonquin Mt Prospect Roads-Des Plaines-Illinois 60016).
La teneur en oléfines est déterminée par la mesure du nombre de brome en application de la norme ASTM D1159, et la teneur en soufre par la méthode ASTM D2622.The benzene content was measured using the UOP 744-86 method referenced in the "Laboratory test methods for petroleum and its products", published by UOP Process Division, (UOP Inc. 20 UOP Plaza-Algonquin Mt Prospect Roads-Des Plains-Illinois 60016).
The olefin content is determined by measuring the number of bromine in application of standard ASTM D1159, and the sulfur content by method ASTM D2622.

Trois précurseurs d'ammoniac ont été utilisés sur une unité pilote d'hydrotraitement pour 100ml de catalyseur, à une température de 200°C, une pression de 26.5x105 Pa, fonctionnant avec un rapport H2/hydrocarbures de 230NI/l, la wh de la charge étant de 1.6h-1.Three ammonia precursors were used on a hydrotreatment pilot unit for 100 ml of catalyst, at a temperature of 200 ° C., a pressure of 26.5 × 10 5 Pa, operating with an H2 / hydrocarbon ratio of 230NI / l, wh of the charge being 1.6h -1 .

Ces précurseurs sont la triéthylèneamine ou TEA, la cyclohexylamine ou CHA et l'éthylènediamine ou EDA.These precursors are triethyleneamine or TEA, cyclohexylamine or CHA and ethylenediamine or EDA.

L'efficacité pour chacun des essais effectués s'apprécie par rapport à la diminution du nombre de composés en C12 formés, à la diminution du nombre de brome et à la diminution de la teneur en soufre. Les résultats sont donnés dans le tableau I ci-après. Nature du précurseur Equivalent N (ppm pds) Teneur en C12 (ppm pds) Indice de brome (mgBr2/100g) Soufre (ppm pds) Azote (ppm pds) Aucun 0 215 8 <0.5 <0.5 TEA 25 11 76 0.5 <0.5 100 12 657 <0.5 <0.5 200 13 758 1 <0.5 CHA 10 5 14 <0.5 <0.5 EDA 25 1 63 <0.5 <0.5 30 1 99 0.5 <0.5 The efficiency for each of the tests carried out is assessed in relation to the decrease in the number of C12 compounds formed, the decrease in the number of bromine and the decrease in the sulfur content. The results are given in Table I below. Nature of the precursor N equivalent (ppm wt) C 12 content (ppm wt) Bromine index (mgBr 2 / 100g) Sulfur (ppm wt) Nitrogen (ppm wt) No 0 215 8 <0.5 <0.5 TEA 25 11 76 0.5 <0.5 100 12 657 <0.5 <0.5 200 13 758 1 <0.5 CHA 10 5 14 <0.5 <0.5 EDA 25 1 63 <0.5 <0.5 30 1 99 0.5 <0.5

Les résultats obtenus indiquent que l'injection de EDA, de TEA ou de CHA comme précurseurs d'ammoniac dans la charge entrant dans une unité d'hydrotraitement permet de notablement diminuer la formation de composés en C12. On peut aisément constater qu'il est possible d'optimiser la quantité d'amine à ajouter à la charge afin de satisfaire simultanément aux spécifications en indice de brome, lié à la concentration d'oléfines, et à la concentration en soufre. On notera que les amines sont totalement décomposées au cours de la réaction puisque la teneur en azote est inférieure à 0.5ppm en poids.The results obtained indicate that the injection of EDA, TEA or CHA as ammonia precursors in the feed entering a hydrotreatment unit makes it possible to significantly reduce the formation of C 12 compounds. It can easily be seen that it is possible to optimize the amount of amine to be added to the feed in order to simultaneously satisfy the specifications in terms of bromine index, linked to the concentration of olefins, and to the sulfur concentration. Note that the amines are completely decomposed during the reaction since the nitrogen content is less than 0.5 ppm by weight.

EXEMPLE IIEXAMPLE II

Le présent exemple vise à souligner l'efficacité du procédé quelles que soient les concentrations relatives de la charge en oléfines et en composés monoaromatiques.The present example aims to emphasize the effectiveness of the process whatever either the relative concentrations of the load in olefins and in compounds monoaromatic.

Dans ce sens deux charges industrielles dont la composition est donnée ci-dessous ont été testées selon la procédure décrite dans l'exemple I mais à des températures de réaction différentes. Leur composition est donnée dans le tableau II ci-après. Charge Nature T°C Nombre de brome (gBr2/100g) Benzène (%pds) Soufre (ppm pds) 1 Coupe C6 essence de pyrolyse 240 30 85 60 2 21% (1) + 79% (2) 200 7 57 12 In this sense, two industrial charges, the composition of which is given below, were tested according to the procedure described in Example I but at different reaction temperatures. Their composition is given in Table II below. Charge Nature T ° C Bromine number (gBr 2 / 100g) Benzene (% wt) Sulfur (ppm wt) 1 C6 cut pyrolysis gasoline 240 30 85 60 2 21% (1) + 79% (2) 200 7 57 12

Dans l'exemple, on utilise la cyclohexylamine ou CHA comme précurseur d'ammoniac. In the example, cyclohexylamine or CHA is used as ammonia precursor.

Les résultats obtenus avec et sans précurseur d'ammoniac pour chacune de ces charges sont donnés dans le tableau III ci-après. Charge CHA (équiv. Molaire N en ppm pds) Production de C12 (ppm pds) Indice de brome (mgBr2/100g) Soufre (ppm pds) Azote (ppm pds) 1 0 489 78 <0.5 <0.5 40 8 83 <0.5 <0.5 2 0 276 11.5 <0.5 <0.5 10 4.5 14 <0.5 <0.5 The results obtained with and without an ammonia precursor for each of these charges are given in Table III below. Charge CHA (Molar equivalent N in ppm wt) C 12 production (ppm wt) Bromine index (mgBr 2 / 100g) Sulfur (ppm wt) Nitrogen (ppm wt) 1 0 489 78 <0.5 <0.5 40 8 83 <0.5 <0.5 2 0 276 11.5 <0.5 <0.5 10 4.5 14 <0.5 <0.5

On constate d'après ce tableau que l'ajout du précurseur d'azote permet quelle que soit la nature de la charge de diminuer la formation de composés en C12 par oligomérisation, tout en maintenant les caractéristiques requises du produit final attendu, y compris en azote, le précurseur se décomposant totalement.It can be seen from this table that the addition of the nitrogen precursor allows whatever the nature of the charge of reducing the formation of compounds into C12 by oligomerization, while maintaining the required characteristics of the expected end product, including nitrogen, the precursor decomposing totally.

Claims (11)

Procédé d'hydrotraitement d'un mélange de composés hydrocarbonés de C4 à C8, riche en oléfines et en composés monoaromatiques, par hydrogénation en présence d'un catalyseur solide caractérisé en ce qu'on introduit un précurseur d'ammoniac dans la charge de composés hydrocarbonés et que le catalyseur comprend au moins un métal de transition supporté sur au moins un oxyde réfractaire.Process for the hydrotreatment of a mixture of hydrocarbon compounds from C4 to C8, rich in olefins and in monoaromatic compounds, by hydrogenation in the presence of a solid catalyst characterized in that an ammonia precursor is introduced into the charge of compounds hydrocarbon and that the catalyst comprises at least one transition metal supported on at least one refractory oxide. Procédé selon la revendication 1 caratérisé en ce qu'on injecte au plus 1000 ppm équivalent molaire azote de précurseur d'ammoniac dans les composés hydrocarbonés.Process according to claim 1, characterized in that one injects with plus 1000 ppm molar equivalent nitrogen precursor ammonia in hydrocarbon compounds. Procédé selon les revendications 1 et 2 caractérisé en ce qu'on injecte de 5 à 1000 ppm équivalent molaire azote de précurseur d'azote, et de préférence de 10 à 200ppm.Process according to Claims 1 and 2, characterized in that 5 to 1000 ppm molar nitrogen equivalent of nitrogen precursor is injected, and preferably 10 to 200 ppm. Procédé selon les revendications 1 à 3 caractérisé en ce que le précurseur d'ammoniac est choisi parmi les composés azotés susceptibles de libérer de l'ammoniac gazeux dans les conditions de l'hydrotraitement.Process according to Claims 1 to 3, characterized in that the ammonia precursor is chosen from nitrogen compounds capable of releasing gaseous ammonia under the conditions of the hydrotreatment. Procédé selon les revendications de 1 à 4 caractérisé en ce que le précurseur d'ammoniac est choisi parmi les amines linéaires et branchées, les polyamines, les imines, et l'urée et ses dérivés.Process according to Claims 1 to 4, characterized in that the ammonia precursor is chosen from linear and branched amines, polyamines, imines, and urea and its derivatives. Procédé selon la revendication 5 caractérisé en ce que les amines et les polyamines sont choisies dans le groupe constitué par les mono, di et trialkylamines comprenant de 1 à 10 atomes de carbone par groupement alkyles, les groupements alkyles étant linéaires ou cycliques, et les polyalkylamines comprenant de 1 à 5 atomes d'azote, chaque groupement alkyles comprenant de 1 à 6 atomes de carbone sous forme linéaire ou ramifiée.Process according to Claim 5, characterized in that the amines and polyamines are chosen from the group consisting of mono, di and trialkylamines comprising from 1 to 10 carbon atoms per alkyl group, the alkyl groups being linear or cyclic, and the polyalkylamines comprising from 1 to 5 nitrogen atoms, each alkyl group comprising from 1 to 6 carbon atoms in linear or branched form. Procédé selon les revendications 5 et 6 caractérisé en ce que les alkylamines et les polyalkylamines sont choisies parmi la méthylamine, l'éthylamine, la propylamine, la butylamine, la pentylamine, l'hexylamine, l'heptylamine, la cyclohexylamine, la cycloheptylamine, la diméthylamine, la diéthylamine la dipropylamine, la dibutylamine, la triméthylamine, la triéthylamine, la tripropylamine , la tributylamine, la méthylènediamine, l'éthylènediamine, la propylènediamine, la butylènediamine, la diméthylènetriamine, la diéthylènetriamine, la dipropylènetriamine, la triéthylènetétramine, la tripropylènetétramine, la tétraéthylènepentamine et la tétrapropylènepentamine, la cyclohexylamine, la triéthylamine, et l'éthylènediamine étant préférées.Process according to Claims 5 and 6, characterized in that the alkylamines and the polyalkylamines are chosen from methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, cyclohexylamine, cycloheptylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, methylenediamine, ethylenediamine, propylenediamine, butylenediamine, dimethylenetriamine, diethylenetriamine, dipropylenetriethylenetrietrietinetriamine triethane tetraethylenepentamine and tetrapropylenepentamine, cyclohexylamine, triethylamine, and ethylenediamine being preferred. Procédé selon les revendications 1 à 7 caractérisé en ce que la réaction d'hydrotraitement est effectuée à une température comprise entre 50 et 400°C, une pression comprise entre 106 Pa et 107Pa, de préférence entre 3x106 Pa et 6x106 Pa, et une vvh variant de 0,5 et 10h-1.Process according to Claims 1 to 7, characterized in that the hydrotreatment reaction is carried out at a temperature between 50 and 400 ° C, a pressure between 10 6 Pa and 10 7 Pa, preferably between 3x10 6 Pa and 6x10 6 Pa, and a vvh varying from 0.5 and 10h -1 . Procédé selon les revendications 1 à 8 caractérisé en ce que l'oxyde réfractaire formant support dans le catalyseur est choisi parmi l'alumine, la silice, la zircone, les silicoalumines, les aluminophosphates, la zircone, la magnésie et les oxydes de titane, rutile et anatase, sous forme amorphe ou cristalline.Process according to Claims 1 to 8, characterized in that the refractory oxide forming a support in the catalyst is chosen from alumina, silica, zirconia, silicoalumines, aluminophosphates, zirconia, magnesia and titanium oxides, rutile and anatase, in amorphous or crystalline form. Procédé selon les revendications 1 à 9 caractérisé en ce que dans le catalyseur, les métaux de transition sont choisis parmi le nickel, le cobalt, le molybdène, le vanadium et le tungstène pris seuls ou en mélange, le nickel seul et les combinaisons nickel/molybdène, cobalt/molybdène et nickel/tungstène étant préférés.Process according to Claims 1 to 9, characterized in that in the catalyst, the transition metals are chosen from nickel, cobalt, molybdenum, vanadium and tungsten taken alone or as a mixture, nickel alone and the nickel / molybdenum, cobalt / molybdenum and nickel / tungsten being preferred. Procédé selon l'une quelconque des revendications 1 à 9 caractérisé en ce que l'ammoniac gazeux formé excédentaire est recyclé dans le gaz de recycle riche en hydrogène.Process according to any one of Claims 1 to 9, characterized in that the excess ammonia gas formed is recycled into the recycle gas rich in hydrogen.
EP00203887A 2000-11-07 2000-11-07 Process for hydrotreatment of hydrocarbon mixtures rich in olefines and aromatics Withdrawn EP1205531A1 (en)

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EP00203887A EP1205531A1 (en) 2000-11-07 2000-11-07 Process for hydrotreatment of hydrocarbon mixtures rich in olefines and aromatics
US10/416,058 US7399402B2 (en) 2000-11-07 2001-11-06 Method for hydrotreatment of a mixture of hydrocarbon compounds, rich in olefins and aromatic compounds
KR1020037006246A KR100591577B1 (en) 2000-11-07 2001-11-06 Method for hydrotreatment of a mixture of hydrocarbon compounds, rich in olefins and aromatic compounds
AU2002219087A AU2002219087A1 (en) 2000-11-07 2001-11-06 Method for hydrotreatment of a mixture of hydrocarbon compounds, rich in olefinsand aromatic compounds
ES01993659T ES2363494T3 (en) 2000-11-07 2001-11-06 HYDRO TREATMENT PROCEDURE OF A MIXTURE OF HYDROCARBON COMPOUNDS, RICH IN OLEFINS AND AROMATIC COMPOUNDS.
PCT/EP2001/012989 WO2002038701A1 (en) 2000-11-07 2001-11-06 Method for hydrotreatment of a mixture of hydrocarbon compounds, rich in olefins and aromatic compounds
JP2002542022A JP4900885B2 (en) 2000-11-07 2001-11-06 Process for hydrotreating a mixture of hydrocarbon compounds rich in olefins and aromatic compounds
EP01993659A EP1334167B1 (en) 2000-11-07 2001-11-06 Method for hydrotreatment of a mixture of hydrocarbon compounds, rich in olefins and aromatic compounds
AT01993659T ATE509997T1 (en) 2000-11-07 2001-11-06 METHOD FOR HYDROTREATING A HYDROCARBON MIXTURE CONTAINING OLEFINS AND AROMATICS

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