EP0554151B1 - Selective hydrogenation process, particularly of steam cracking gasolines, with a catalyst in several sequentially used beds - Google Patents

Selective hydrogenation process, particularly of steam cracking gasolines, with a catalyst in several sequentially used beds Download PDF

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EP0554151B1
EP0554151B1 EP93400164A EP93400164A EP0554151B1 EP 0554151 B1 EP0554151 B1 EP 0554151B1 EP 93400164 A EP93400164 A EP 93400164A EP 93400164 A EP93400164 A EP 93400164A EP 0554151 B1 EP0554151 B1 EP 0554151B1
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Prior art keywords
bed
charge
catalyst
product
beds
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German (de)
French (fr)
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EP0554151A1 (en
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Jean Cosyns
Patrick Sarrazin
Jean-Paul Boitiaux
Charles Cameron
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IFP Energies Nouvelles IFPEN
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    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/06—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a selective hydrogenation of the diolefins

Definitions

  • the present invention relates to a hydrogenation process and more particularly to a process for the selective hydrogenation of diolefins in liquid hydrocarbon fractions such as, for example, steam cracked gasolines.
  • liquid hydrocarbon fractions such as, for example, steam cracked gasolines.
  • These essences indeed contain gum-generating compounds that are diolefins mixed with olefinic compounds and aromatic compounds. To recover these olefinic compounds and these aromatic compounds, it is necessary to selectively hydrogenate the diolefins.
  • Such treatments are generally carried out on metal catalysts deposited on an amorphous or crystalline support.
  • the metals used are the Group VIII metals and among these, nickel and palladium can be noted.
  • the implementation of the hydrogenation operation itself involves a heat extraction system because the exotherm is such that the catalyst would be damaged by the excessively high temperatures which prevail at the outlet of the catalyst bed.
  • This extraction of calories can be done by exchange with a heat transfer fluid in a reactor-exchanger, the catalyst being maintained in the tubes and the heat transfer fluid being debited from the grille side.
  • Such an implementation, called isothermal is complicated and requires the use of very expensive reactors.
  • An improvement consists in separating the catalyst into two beds and cooling the effluent from the first bed with a quenching liquid consisting of cold hydrogenated product.
  • the object of the invention is therefore to extend the operating time of the catalyst payload by gradually bringing the entire catalyst charge into service instead of using it entirely from the start. It has in fact been surprisingly found that it is better to use the minimum quantity of catalyst rather than having a substantial excess at the start of operation, as is commonly done in order to compensate for the deactivation of the first part. bed.
  • the process which is the subject of the invention therefore consists in distributing the catalyst into several beds and preferably in the same reactor, but putting these beds into service successively, by adding a new catalyst bed at the head as soon as the need arises. is felt, that is to say when the performance of the mass of catalyst in operation is insufficient to give a product to the specifications.
  • the invention is a process for the hydrogenation of hydrocarbon feedstock by contact with p catalytic beds n 1 ... n i ... np, said beds being separated and containing the same catalyst, process characterized in that the feedstock is introduced into the bed n p and the resulting product p p is extracted, that, when the product p p does not reach the required quality, the introduction of the load in bed np is stopped, and that simultaneously the load is introduced into bed n p-1 , the product obtained p p-1 being introduced into bed n p , and that then, generally, when the product p p reaches the minimum performance threshold, the introduction of the load into the bed ni is stopped, at the same time the load is introduced into the bed n i-1 , the product obtained p i-1 being introduced into the bed n i , and so on until i has taken all the integer values up to 1.
  • FIG. 1 represents the process applied with several separate reactors, FIG. 2 in a single reactor.
  • the known technique consisted in using an entire mass of catalyst to obtain a product p p having the required specifications, for a cycle time D (or operating time).
  • the mass of catalyst or an amount less than this mass is divided into p beds (n 1 , n i , n p ) distributed in 1 or more reactors and each containing at least the minimum quantity of catalyst necessary for obtaining the required specifications.
  • the supply of the load is moved to the bed n i-1 , located upstream of the bed nor so that the load to be treated successively crosses the bed n i-1 of new catalyst, then the product from this bed through the spent catalyst bed ni, the product obtained pi passing through the spent catalyst bed n i + 1 etc ... until the bed np either crossed, the product p p then being obtained.
  • valve 40 when p 4 reaches its threshold S, the valve 40 is closed (preferably progressively), thus stopping the introduction of charge into n 4 and in the same time, the valve 30 is open so as to supply the bed n 3 with the load via the pipe 3.
  • the product p 3 obtained after passage of the charge over n 3 , passes over the bed n 4 (downstream). It appears p 4 of bed no 4 .
  • the procedure is the same as above, forming the valve 30 while simultaneously opening the valve 20 for supplying the bed n 2 through the pipe 2.
  • the product p 2 from this bed then passes over the bed n 3 , the product p3 from n 3 passes over the bed n4 and the final product p4 is extracted.
  • the hydrogen necessary for the reaction is brought for example by means of the pipes 41, 31, 21, 11 successively put into service on the reaction beds.
  • the use of a single reactor is particularly advantageous in terms of costs, but the reactor can only operate with a downflow, the bed n p having to be the lowest and the bed n 1 the top.
  • the operator may also prefer to use smaller quantities of catalyst (total mass less than ) for comparable cycle times.
  • catalyst test unit comprising 4 reactors which can operate in series, the effluent from the first being transferred to the second then to the third and then to the fourth.
  • reactors modeling each bed consist of a steel tube 3 cm in diameter. Each of these reactors can be heated by an electric oven which makes it possible to maintain the desired temperature in each of the beds.
  • All of the reactors can be used as described above, that is to say N ° 1, N ° 2, N ° 3, N ° 4 but a device also makes it possible to use the reactor 4 only or else 3 and 4 in series, or 2, 3 and 4 in series.
  • catalyst LD 265 from the company Procatalyse containing 0.3% of palladium supported on alumina in the 4 reactors arranged in series at a rate of 100 cm 3 per reactor.
  • This catalyst is reduced by hydrogen delivered for 6 hours at 150 ° C at a rate of 40 l / h.
  • the performances are measured by the variation of the maleic anhydride index (AVM) between the inlet of the first reactor and the outlet of the fourth.
  • the temperature is set at 80 ° C in all of the reactors at the start of operation and then regularly increased to 120 ° C to restore the conversion when it decreases.
  • the load gives an AVM of 106, the AVMs of the products are given as a function of time as well as the operating temperature in table 1.
  • Table 1 Walking time in hours
  • Temperature MAV output 50 80 ⁇ 2 100 80 ⁇ 2 200 80 ⁇ 2 500 80 2.2 750 80 2.3 820 80 2.8 950 80 3.8 1160 95 ⁇ 2 1300 95 4 1400 110 ⁇ 2 1540 110 5 1600 120 ⁇ 2 1800 120 8
  • a new reactor is put into service when the assembly in operation no longer makes it possible to obtain an AVM of less than 3 at output for a temperature of 80 ° C. Then, the temperature of the four reactors is gradually increased to restore performance.
  • the AVMs of the products are given as well as the arrangement of the reactors and the operating temperature as a function of time in Table 2.
  • Table 2 Walking time in hours Arrangement Temperature MAV output 50 4 80 ⁇ 2 100 4 80 ⁇ 2 200 4 80 2.4 500 4 80 2.8 600 4 80 3.8 700 3.4 80 ⁇ 2 800 3.4 80 ⁇ 2 1000 3.4 80 2.5 1200 3.4 80 3.2 1300 2,3,4 80 ⁇ 2 1400 2,3,4 80 ⁇ 2 1600 2,3,4 80 2.7 1800 2,3,4 80 3 1900 1,2,3,4 80 ⁇ 2 2000 1,2,3,4 80 ⁇ 2 2200 1,2,3,4 80 2.5 2400 1,2,3,4 80 3.8 2800 1,2,3,4 90 ⁇ 2 2950 1,2,3,4 90 3.7 3000 1,2,3,4 95 ⁇ 2 3280 1,2,3,4 95 2.6 3300 1,2,3,4 100 ⁇ 2 3480 1,2,3,4 100 3 3500 1,2,3,4 115 ⁇ 2 2590 1,2,3,4 115 3.7 3600 1,2,3,4 120 ⁇ 2
  • catalyst LD 241 from the company Procatalyse containing 10% of nickel supported on alumina in the 4 reactors arranged in series at the rate of 100 cm 3 per reactor.
  • This catalyst is reduced by hydrogen delivered for 15 hours at 400 ° C at a rate of 40 l / h.
  • the activity of the catalyst is then measured under the same conditions as in Example 1.
  • the AVMs of the products are given as a function of time as well as the operating temperature in table 3.
  • Table 3 Walking time in hours Temperature MAV output 40 80 ⁇ 2 70 80 ⁇ 2 100 80 2 400 80 4.2 420 95 ⁇ 2 470 95 2.7 500 95 3.2 520 110 ⁇ 2 540 110 ⁇ 2 600 110 3.1 620 120 ⁇ 2 640 120 ⁇ 2 650 120 2.5 670 120 2.9 700 120 3.2
  • Table 4 shows the AVM of the products as well as the arrangement of the reactors and the operating temperature as a function of time.

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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)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

La présente invention concerne un procédé d'hydrogénation et plus particulièrement un procédé d'hydrogénation sélective des dioléfines dans les coupes hydrocarbures liquides comme par exemple les essences de vapocraquage. Ces essences contiennent en effet des composés générateurs de gommes que sont les dioléfines en mélange avec des composés oléfiniques et des composés aromatiques. Pour valoriser ces composés oléfiniques et ces composés aromatiques, il est nécessaire d'hydrogéner sélectivement les dioléfines.The present invention relates to a hydrogenation process and more particularly to a process for the selective hydrogenation of diolefins in liquid hydrocarbon fractions such as, for example, steam cracked gasolines. These essences indeed contain gum-generating compounds that are diolefins mixed with olefinic compounds and aromatic compounds. To recover these olefinic compounds and these aromatic compounds, it is necessary to selectively hydrogenate the diolefins.

De tels traitements sont généralement effectués sur des catalyseurs métalliques déposés sur support amorphe ou cristallin. Les métaux utilisés sont les métaux du groupe VIII et parmi ceux-ci, on peut noter le nickel et le palladium.Such treatments are generally carried out on metal catalysts deposited on an amorphous or crystalline support. The metals used are the Group VIII metals and among these, nickel and palladium can be noted.

Le caractère très instable de ces essences de pyrolyse en rend le traitement peu aisé car parallèlement à l'hydrogénation se produit sur le catalyseur une réaction de polymérisation qui provoque un colmatage et une désactivation du catalyseur. Pour compenser cette perte d'activité, on augmente progressivement la température opératoire mais cette façon de procéder augmente encore la vitesse à laquelle les dépôts polymériques se font. En conséquence, il est nécessaire de stopper périodiquement l'opération afin de procéder à un brûlage du catalyseur pour retrouver son activité initiale. Cet arrêt représente une perte réelle de production et la combustion doit être conduite très précisément pour éviter la dégradation irréversible des propriétés du catalyseur. Toute amélioration du procédé qui permettra d'augmenter la durée de cycle, c'est-à-dire la période entre deux combustions augmentera sensiblement la qualité de celui-ci.The very unstable nature of these pyrolysis essences makes their treatment not very easy because in parallel with the hydrogenation occurs on the catalyst a polymerization reaction which causes clogging and deactivation of the catalyst. To compensate for this loss of activity, the operating temperature is gradually increased, but this procedure further increases the speed at which the polymeric deposits are made. Consequently, it is necessary to periodically stop the operation in order to proceed with a burning of the catalyst in order to regain its initial activity. This shutdown represents a real loss of production and combustion must be carried out very precisely to avoid irreversible degradation of the properties of the catalyst. Any improvement in the process which will make it possible to increase the cycle time, that is to say the period between two combustions, will appreciably increase the quality of the latter.

La mise en oeuvre de l'opération d'hydrogénation elle-même implique un système d'extraction de calories car l'exothermicité est telle que le catalyseur serait endommagé par les températures trop élevées qui règneraient à la sortie du lit de catalyseur. Cette extraction des calories peut se faire par échange avec un fluide caloporteur dans un réacteur-échangeur, le catalyseur étant maintenu dans les tubes et le fluide caloporteur étant débité du côté calandre. Une telle mise en oeuvre, dite isotherme est compliquée et oblige à utiliser des réacteurs très onéreux.The implementation of the hydrogenation operation itself involves a heat extraction system because the exotherm is such that the catalyst would be damaged by the excessively high temperatures which prevail at the outlet of the catalyst bed. This extraction of calories can be done by exchange with a heat transfer fluid in a reactor-exchanger, the catalyst being maintained in the tubes and the heat transfer fluid being debited from the grille side. Such an implementation, called isothermal is complicated and requires the use of very expensive reactors.

On préfère généralement utiliser des réacteurs chambres et le contrôle de l'exothermicité de la réaction est réalisé par recyclage important de produit hydrogéné en tête de lit. Une amélioration consiste à séparer le catalyseur en deux lits et refroidir l'effluent du premier lit par un liquide de trempe constitué par du produit hydrogéné froid.It is generally preferred to use chamber reactors and the control of the exothermicity of the reaction is carried out by significant recycling of hydrogenated product at the head of the bed. An improvement consists in separating the catalyst into two beds and cooling the effluent from the first bed with a quenching liquid consisting of cold hydrogenated product.

Néanmoins, une telle mise en oeuvre n'est pas entièrement satisfaisante car l'ensemble du catalyseur est soumis à la polymérisation, ce qui provoque dans beaucoup de cas un arrêt prématuré de l'installation pour perte de charge excessive à l'entrée de la section.However, such an implementation is not entirely satisfactory since the whole of the catalyst is subjected to polymerization, which in many cases causes a premature shutdown of the installation for excessive pressure drop at the inlet of the section.

L'objet de l'invention est donc de prolonger la durée de fonctionnement de la charge utile de catalyseur en mettant en service progressivement l'ensemble de la charge de catalyseur au lieu de la mettre en oeuvre en totalité dès le démarrage. Il a été en effet trouvé de façon surprenante qu'il valait mieux mettre en oeuvre la quantité minimale de catalyseur plutôt que d'avoir un excès substantiel en début de fonctionnement comme cela se pratique couramment dans le but de compenser la désactivation de la première partie du lit.The object of the invention is therefore to extend the operating time of the catalyst payload by gradually bringing the entire catalyst charge into service instead of using it entirely from the start. It has in fact been surprisingly found that it is better to use the minimum quantity of catalyst rather than having a substantial excess at the start of operation, as is commonly done in order to compensate for the deactivation of the first part. bed.

Le procédé, objet de l'invention consiste donc à répartir le catalyseur en plusieurs lits et de préférence dans le même réacteur, mais de mettre ces lits en service successivement, en ajoutant un lit de catalyseur neuf en tête dès que le besoin s'en fait sentir, c'est-à-dire quand la performance de la masse de catalyseur en opération est insuffisante pour donner un produit aux spécifications.The process which is the subject of the invention therefore consists in distributing the catalyst into several beds and preferably in the same reactor, but putting these beds into service successively, by adding a new catalyst bed at the head as soon as the need arises. is felt, that is to say when the performance of the mass of catalyst in operation is insufficient to give a product to the specifications.

Plus précisément, l'invention est un procédé d'hydrogénation de charge hydrocarbonée par contact avec p lits catalytiques n1...ni...np, lesdits lits étant séparés et contenant le même catalyseur, procédé caractérisé en ce que la charge est introduite dans le lit np et le produit résultant pp est extrait, que, lorsque le produit pp n'atteint pas la qualité demandée, l'introduction de la charge dans le lit np est stoppée, et que, simultanément la charge est introduite dans le lit np-1, le produit obtenu pp-1 étant introduit dans le lit np, et que ensuite, de façon générale, lorsque le produit pp atteint le seuil minimum de performance, l'introduction de la charge dans le lit ni est stoppée, dans le même temps la charge est introduite dans le lit ni-1, le produit obtenu pi-1 étant introduit dans le lit ni, et ainsi de suite jusqu'à ce que i ait pris toutes les valeurs entières jusqu'à 1.More specifically, the invention is a process for the hydrogenation of hydrocarbon feedstock by contact with p catalytic beds n 1 ... n i ... np, said beds being separated and containing the same catalyst, process characterized in that the feedstock is introduced into the bed n p and the resulting product p p is extracted, that, when the product p p does not reach the required quality, the introduction of the load in bed np is stopped, and that simultaneously the load is introduced into bed n p-1 , the product obtained p p-1 being introduced into bed n p , and that then, generally, when the product p p reaches the minimum performance threshold, the introduction of the load into the bed ni is stopped, at the same time the load is introduced into the bed n i-1 , the product obtained p i-1 being introduced into the bed n i , and so on until i has taken all the integer values up to 1.

L'invention sera mieux comprise en se référant à la description des figures 1 et 2.The invention will be better understood by referring to the description of Figures 1 and 2.

La figure 1 représente le procédé appliqué avec plusieurs réacteurs séparés, la figure 2 dans un seul réacteur.FIG. 1 represents the process applied with several separate reactors, FIG. 2 in a single reactor.

Antérieurement à l'invention, la technique connue consistait à utiliser une entière masse

Figure imgb0001
de catalyseur pour obtenir un produit pp présentant les spécifications requises, ce pour une durée de cycle D (ou durée de fonctionnement).Prior to the invention, the known technique consisted in using an entire mass
Figure imgb0001
of catalyst to obtain a product p p having the required specifications, for a cycle time D (or operating time).

Lorsque le produit pp présentait des spécifications inférieures à celles requises (c'est-à-dire que le produit pp atteint le seuil minimum S de performance), on arrêtait le réacteur et régénérait le catalyseur.When the product p p had specifications lower than those required (that is to say that the product p p reached the minimum performance threshold S), the reactor was stopped and the catalyst was regenerated.

Selon l'invention, la masse

Figure imgb0001
de catalyseur ou une quantité inférieure à cette masse est fractionnée en p lits (n1, ni, np) répartis dans 1 ou plusieurs réacteurs et contenant chacun au moins la quantité minimale de catalyseur nécessaire à l'obtention des spécifications requises. Chaque fois que le produit pp n'atteint plus la qualité demandée, l'alimentation de la charge est déplacée vers le lit ni-1, situé en amont du lit ni de façon à ce que la charge à traiter traverse successivement le lit ni-1 de catalyseur neuf, puis le produit, issu de ce lit travers le lit de catalyseur usé ni, le produit obtenu pi traversant le lit de catalyseur usé ni+1 etc... jusqu'à ce que le lit np soit traversé, le produit pp étant alors obtenu.According to the invention, the mass
Figure imgb0001
of catalyst or an amount less than this mass is divided into p beds (n 1 , n i , n p ) distributed in 1 or more reactors and each containing at least the minimum quantity of catalyst necessary for obtaining the required specifications. Each time that the product p p no longer reaches the required quality, the supply of the load is moved to the bed n i-1 , located upstream of the bed nor so that the load to be treated successively crosses the bed n i-1 of new catalyst, then the product from this bed through the spent catalyst bed ni, the product obtained pi passing through the spent catalyst bed n i + 1 etc ... until the bed np either crossed, the product p p then being obtained.

Plus précisément, en se référant aux figures 1 et 2 dans lesquelles p = 4, lorsque p4 atteint son seuil S, la vanne 40 est fermée (de préférence progressivement), arrêtant ainsi l'introduction de charge dans n4 et dans le même temps, la vanne 30 est ouverte de façon à alimenter le lit n3 avec la charge par la canalisation 3.More precisely, with reference to FIGS. 1 and 2 in which p = 4, when p 4 reaches its threshold S, the valve 40 is closed (preferably progressively), thus stopping the introduction of charge into n 4 and in the same time, the valve 30 is open so as to supply the bed n 3 with the load via the pipe 3.

Le produit p3, obtenu après passage de la charge sur n3, passe sur le lit n4 (en aval). Il ressort p4 du lit n4. Lorsqu'on détecte (par mesure d'une spécification et comparaison avec la spécification demandée pour la qualité) que p4 ne présente plus la qualité demandée, on procède de la même façon que précédemment, en formant la vanne 30 tandis que simultanément on ouvre la vanne 20 pour alimenter le lit n2 par la canalisation 2. Le produit p2 issu de ce lit passe ensuite sur le lit n3, le produit p3 issu de n3 passe sur le lit n4 et le produit final p4 est extrait.The product p 3 , obtained after passage of the charge over n 3 , passes over the bed n 4 (downstream). It appears p 4 of bed no 4 . When it is detected (by measuring a specification and comparison with the requested specification for the quality) that p 4 no longer exhibits the requested quality, the procedure is the same as above, forming the valve 30 while simultaneously opening the valve 20 for supplying the bed n 2 through the pipe 2. The product p 2 from this bed then passes over the bed n 3 , the product p3 from n 3 passes over the bed n4 and the final product p4 is extracted.

Et ainsi de suite jusqu'au dernier lit n1 qui est alimenté par une canalisation 1 munie d'une vanne 10.And so on until the last bed n 1 which is supplied by a pipe 1 provided with a valve 10.

L'hydrogène nécessaire à la réaction est amené par exemple au moyen des canalisations 41, 31, 21, 11 mises successivement en service sur les lits en réaction.The hydrogen necessary for the reaction is brought for example by means of the pipes 41, 31, 21, 11 successively put into service on the reaction beds.

On a représenté 4 lits pour illustrer l'invention, on conçoit qu'elle s'applique à p lits.4 beds have been shown to illustrate the invention, it can be understood that it applies to p beds.

Lorsque le dernier lit, n1 est mis en service et que le produit pp obtenu présente une qualité inférieure à celle demandée, on peut alors, de façon avantageuse, augmenter progressivement la température de la masse totale de catalyseur de façon à obtenir à nouveau et maintenir la qualité demandée sur pp, ceci jusqu'à la désactivation complète du catalyseur.When the last bed, n 1 is put into service and the product p p obtained has a quality lower than that required, it is then possible, advantageously, to gradually increase the temperature of the total mass of catalyst so as to obtain again and maintain the requested quality on p p , until the catalyst is completely deactivated.

L'utilisation d'un seul réacteur est particulièrement avantageuse au niveau des coûts, mais le réacteur ne peut fonctionner qu'avec un écoulement descendant, le lit np devant être le plus bas et le lit n1 le puys haut.The use of a single reactor is particularly advantageous in terms of costs, but the reactor can only operate with a downflow, the bed n p having to be the lowest and the bed n 1 the top.

La demanderesse a ainsi pu constater que de façon surprenante (montrée par les exemples), par rapport à un procédé d'hydrogénation avec un lit unique d'une masse

Figure imgb0001
de catalyseur, on obtient pour une même masse
Figure imgb0001
de catalyseur totale (somme de tous les lits n1 à np) des durées de cycle notablement plus importantes (gain de 57 % selon l'exemple).The Applicant has thus been able to note that, surprisingly (shown by the examples), compared with a hydrogenation process with a single bed of a mass
Figure imgb0001
of catalyst, we obtain for the same mass
Figure imgb0001
total catalyst (sum of all beds n1 to np) significantly longer cycle times (gain of 57% according to the example).

L'exploitant peut également préférer utiliser des quantités de catalyseur moins importantes (masse totale inférieure à

Figure imgb0001
) pour des durées de cycle comparables.The operator may also prefer to use smaller quantities of catalyst (total mass less than
Figure imgb0001
) for comparable cycle times.

Les exemples suivants illustrent l'invention.The following examples illustrate the invention.

EXEMPLE 1 (comparaison)EXAMPLE 1 (comparison)

On dispose d'une unité de test de catalyseur comportant 4 réacteurs pouvant fonctionner en série, l'effluent du premier étant transféré dans le second puis dans le troisième puis dans le quatrième.There is a catalyst test unit comprising 4 reactors which can operate in series, the effluent from the first being transferred to the second then to the third and then to the fourth.

Ces réacteurs modélisant chaque lit sont constitués par un tube en acier de 3 cm de diamètre. Chacun de ces réacteurs peut être chauffé par un four électrique qui permet de maintenir la température désirée dans chacun des lits.These reactors modeling each bed consist of a steel tube 3 cm in diameter. Each of these reactors can be heated by an electric oven which makes it possible to maintain the desired temperature in each of the beds.

On peut utiliser l'ensemble des réacteurs comme décrit ci-dessus, c'est-à-dire N°1, N°2, N°3, N°4 mais un dispositif permet également d'utiliser le réacteur 4 seulement ou bien 3 et 4 en série, ou bien 2, 3 et 4 en série.All of the reactors can be used as described above, that is to say N ° 1, N ° 2, N ° 3, N ° 4 but a device also makes it possible to use the reactor 4 only or else 3 and 4 in series, or 2, 3 and 4 in series.

On dispose 400 cm3 de catalyseur LD 265 de la Société Procatalyse contenant 0,3 % de palladium supporté sur alumine dans les 4 réacteurs disposés en série à raison de 100 cm3 par réacteur.There is 400 cm 3 of catalyst LD 265 from the company Procatalyse containing 0.3% of palladium supported on alumina in the 4 reactors arranged in series at a rate of 100 cm 3 per reactor.

On réduit ce catalyseur par de l'hydrogène débité pendant 6 heures à 150°C à raison de 40 l/h.This catalyst is reduced by hydrogen delivered for 6 hours at 150 ° C at a rate of 40 l / h.

On mesure alors l'activité hydrogénante de ces 400 cm3 de catalyseur vis-à-vis des dioléfines contenues dans une essence de vapocraquage ayant les caractéristiques suivantes :

  • Intervalle de distillation : 39-181 °C
  • Densité : 0,834
  • Soufre : 150 ppm
  • Diènes : 16 % Poids
  • Oléfines : 4 % Poids
  • Aromatiques : 68 % Poids
  • Paraffines : 12 % Poids
The hydrogenating activity of these 400 cm 3 of catalyst is then measured with respect to the diolefins contained in a steam cracking gasoline having the following characteristics:
  • Distillation range: 39-181 ° C
  • Density: 0.834
  • Sulfur: 150 ppm
  • Dienes: 16% Weight
  • Olefins: 4% Weight
  • Aromatics: 68% Weight
  • Paraffins: 12% Weight

Les conditions de test sont les suivantes :

  • Pression : 30 bar
  • Température : 80 °C initialement
  • Débit d'hydrocarbure : 500 cm3/h
  • Débit d'hydrogène : 100 l/h
The test conditions are as follows:
  • Pressure: 30 bar
  • Temperature: 80 ° C initially
  • Hydrocarbon flow: 500 cm 3 / h
  • Hydrogen flow: 100 l / h

Les performances sont mesurées par la variation de l'indice d'anhydride maléique (MAV) entre l'entrée du premier réacteur et la sortie du quatrième. La température est fixée à 80 °C dans l'ensemble des réacteurs en début de fonctionnement puis régulièrement augmentée jusqu'à 120 °C pour rétablir la conversion lorsque celle-ci diminue. La charge donne une MAV de 106, les MAV des produits sont données en fonction du temps ainsi que la température de fonctionnement dans le tableau 1. Tableau 1 Temps de marche en heures Température MAV sortie 50 80 < 2 100 80 < 2 200 80 < 2 500 80 2,2 750 80 2,3 820 80 2,8 950 80 3,8 1160 95 < 2 1300 95 4 1400 110 < 2 1540 110 5 1600 120 < 2 1800 120 8 The performances are measured by the variation of the maleic anhydride index (AVM) between the inlet of the first reactor and the outlet of the fourth. The temperature is set at 80 ° C in all of the reactors at the start of operation and then regularly increased to 120 ° C to restore the conversion when it decreases. The load gives an AVM of 106, the AVMs of the products are given as a function of time as well as the operating temperature in table 1. Table 1 Walking time in hours Temperature MAV output 50 80 <2 100 80 <2 200 80 <2 500 80 2.2 750 80 2.3 820 80 2.8 950 80 3.8 1160 95 <2 1300 95 4 1400 110 <2 1540 110 5 1600 120 <2 1800 120 8

On peut voir sur ce tableau que l'arrangement en quatre lits successivement traversés permet de maintenir le produit en sortie de section réactionnelle à une MAV inférieure à 3 pendant environ 1500 heures.It can be seen from this table that the arrangement in four successively crossed beds makes it possible to maintain the product at the outlet of the reaction section at an AVM less than 3 for approximately 1500 hours.

EXEMPLE 2 (selon l'invention)EXAMPLE 2 (according to the invention)

On utilise maintenant l'installation de test selon sa deuxième possibilité. On charge donc les quatre réacteurs avec les mêmes quantités du même catalyseur et on active l'ensemble de la même façon que ci-dessus puis l'on mesure les performances en fonction du temps de la même façon que ci-dessus.We now use the test facility according to its second possibility. The four reactors are therefore loaded with the same quantities of the same catalyst and the assembly is activated in the same way as above, then the performance is measured as a function of time in the same way as above.

Cependant, on ne met en oeuvre les réacteurs que successivement dans l'ordre suivant :

  • Réacteur 4,
  • Réacteur 3 + réacteur 4,
  • Réacteur 2 + réacteur 3 + réacteur 4,
  • Réacteur 1 + réacteur 2 + réacteur 3 + réacteur 4.
However, the reactors are only operated successively in the following order:
  • Reactor 4,
  • Reactor 3 + reactor 4,
  • Reactor 2 + reactor 3 + reactor 4,
  • Reactor 1 + reactor 2 + reactor 3 + reactor 4.

Un nouveau réacteur est mis en service lorsque l'ensemble en opération ne permet plus d'obtenir une MAV inférieure à 3 en sortie pour une température de 80 °C. Ensuite, la température des quatre réacteurs est progressivement augmentée pour rétablir la performance.A new reactor is put into service when the assembly in operation no longer makes it possible to obtain an AVM of less than 3 at output for a temperature of 80 ° C. Then, the temperature of the four reactors is gradually increased to restore performance.

Les MAV des produits sont données ainsi que l'agencement des réacteurs et la température de fonctionnement en fonction du temps dans le tableau 2. Tableau 2 Temps de marche en heure Arrangement Température MAV sortie 50 4 80 < 2 100 4 80 < 2 200 4 80 2,4 500 4 80 2,8 600 4 80 3,8 700 3,4 80 < 2 800 3,4 80 < 2 1000 3,4 80 2,5 1200 3,4 80 3,2 1300 2,3,4 80 < 2 1400 2,3,4 80 < 2 1600 2,3,4 80 2,7 1800 2,3,4 80 3 1900 1,2,3,4 80 < 2 2000 1,2,3,4 80 < 2 2200 1,2,3,4 80 2,5 2400 1,2,3,4 80 3,8 2800 1,2,3,4 90 < 2 2950 1,2,3,4 90 3,7 3000 1,2,3,4 95 < 2 3280 1,2,3,4 95 2,6 3300 1,2,3,4 100 < 2 3480 1,2,3,4 100 3 3500 1,2,3,4 115 < 2 2590 1,2,3,4 115 3,7 3600 1,2,3,4 120 < 2 The AVMs of the products are given as well as the arrangement of the reactors and the operating temperature as a function of time in Table 2. Table 2 Walking time in hours Arrangement Temperature MAV output 50 4 80 <2 100 4 80 <2 200 4 80 2.4 500 4 80 2.8 600 4 80 3.8 700 3.4 80 <2 800 3.4 80 <2 1000 3.4 80 2.5 1200 3.4 80 3.2 1300 2,3,4 80 <2 1400 2,3,4 80 <2 1600 2,3,4 80 2.7 1800 2,3,4 80 3 1900 1,2,3,4 80 <2 2000 1,2,3,4 80 <2 2200 1,2,3,4 80 2.5 2400 1,2,3,4 80 3.8 2800 1,2,3,4 90 <2 2950 1,2,3,4 90 3.7 3000 1,2,3,4 95 <2 3280 1,2,3,4 95 2.6 3300 1,2,3,4 100 <2 3480 1,2,3,4 100 3 3500 1,2,3,4 115 <2 2590 1,2,3,4 115 3.7 3600 1,2,3,4 120 <2

On voit que la mise en oeuvre progressive de la même quantité de catalyseur que dans l'exemple 1 permet une durée de fonctionnement satisfaisante bien supérieure.It can be seen that the gradual use of the same quantity of catalyst as in Example 1 allows a much longer satisfactory operating time.

EXEMPLE 3 (Comparatif)EXAMPLE 3 (Comparative)

On dispose 400 cm3 de catalyseur LD 241 de la Société Procatalyse contenant 10 % de nickel supporté sur alumine dans les 4 réacteurs disposés en série à raison de 100 cm3 par réacteur.There is 400 cm 3 of catalyst LD 241 from the company Procatalyse containing 10% of nickel supported on alumina in the 4 reactors arranged in series at the rate of 100 cm 3 per reactor.

On réduit ce catalyseur par de l'hydrogène débité pendant 15 heures à 400 °C à raison de 40 l/h.This catalyst is reduced by hydrogen delivered for 15 hours at 400 ° C at a rate of 40 l / h.

On mesure alors l'activité du catalyseur dans les mêmes conditions que dans l'exemple 1.The activity of the catalyst is then measured under the same conditions as in Example 1.

Les MAV des produits sont données en fonction du temps ainsi que la température de fonctionnement dans le tableau 3. Tableau 3 Temps de marche en heures Température MAV sortie 40 80 < 2 70 80 < 2 100 80 2 400 80 4,2 420 95 < 2 470 95 2,7 500 95 3,2 520 110 < 2 540 110 < 2 600 110 3,1 620 120 < 2 640 120 < 2 650 120 2,5 670 120 2,9 700 120 3,2 The AVMs of the products are given as a function of time as well as the operating temperature in table 3. Table 3 Walking time in hours Temperature MAV output 40 80 <2 70 80 <2 100 80 2 400 80 4.2 420 95 <2 470 95 2.7 500 95 3.2 520 110 <2 540 110 <2 600 110 3.1 620 120 <2 640 120 <2 650 120 2.5 670 120 2.9 700 120 3.2

On peut voir sur ce tableau que l'arrangement en quatre lits successivement traversés permet de maintenir le produit en sortie de section réactionnelle à une MAV inférieure à 3 pendant environ 700 heures.It can be seen from this table that the arrangement in four successively crossed beds makes it possible to maintain the product at the outlet of the reaction section at an AVM less than 3 for approximately 700 hours.

EXEMPLE 4 (selon l'invention)EXAMPLE 4 (according to the invention)

On utilise maintenant le même catalyseur LD 241 mais selon l'arrangement de l'exemple 2.The same LD 241 catalyst is now used, but according to the arrangement of Example 2.

Le tableau 4 présente la MAV des produits ainsi que l'arrangement des réacteurs et la température de fonctionnement en fonction du temps.Table 4 shows the AVM of the products as well as the arrangement of the reactors and the operating temperature as a function of time.

On voit que la mise en oeuvre progressive de la même quantité de catalyseur que dans l'exemple 3 permet une durée de fonctionnement satisfaisante bien supérieure. Tableau 4 Temps de marche en heures Arrangement Température MAV sortie 40 4 80 < 2 80 4 80 < 2 100 4 80 2 300 4 80 4 320 3,4 80 < 2 340 3,4 80 < 2 370 3,4 80 2,8 400 3,4 80 3,4 420 2,3,4 80 < 2 450 2,3,4 80 < 2 480 2,3,4 80 2,1 500 2,3,4 80 2,9 520 1,2,3,4 80 < 2 560 1,2,3,4 80 < 2 600 1,2,3,4 80 2,4 640 1,2,3,4 80 3,4 650 1,2,3,4 95 < 2 680 1,2,3,4 95 < 2 700 1,2,3,4 95 2,5 740 1,2,3,4 95 3,4 760 1,2,3,4 110 < 2 800 1,2,3,4 110 < 2 860 1,2,3,4 110 3,2 880 1,2,3,4 110 < 2 900 1,2,3,4 110 < 2 930 1,2,3,4 120 2,9 950 1,2,3,4 120 < 2 990 1,2,3,4 120 < 2 1020 1,2,3,4 120 2,5 1100 1,2,3,4 120 2,9 It can be seen that the gradual use of the same quantity of catalyst as in Example 3 allows a much longer satisfactory operating time. Table 4 Walking time in hours Arrangement Temperature MAV output 40 4 80 <2 80 4 80 <2 100 4 80 2 300 4 80 4 320 3.4 80 <2 340 3.4 80 <2 370 3.4 80 2.8 400 3.4 80 3.4 420 2,3,4 80 <2 450 2,3,4 80 <2 480 2,3,4 80 2.1 500 2,3,4 80 2.9 520 1,2,3,4 80 <2 560 1,2,3,4 80 <2 600 1,2,3,4 80 2.4 640 1,2,3,4 80 3.4 650 1,2,3,4 95 <2 680 1,2,3,4 95 <2 700 1,2,3,4 95 2.5 740 1,2,3,4 95 3.4 760 1,2,3,4 110 <2 800 1,2,3,4 110 <2 860 1,2,3,4 110 3.2 880 1,2,3,4 110 <2 900 1,2,3,4 110 <2 930 1,2,3,4 120 2.9 950 1,2,3,4 120 <2 990 1,2,3,4 120 <2 1020 1,2,3,4 120 2.5 1100 1,2,3,4 120 2.9

Claims (6)

  1. A process for the hydrogenation of a hydrocarbon charge by contact with p catalytic beds n1...ni...np, said beds being separate and containing the same catalyst, the process being characterised in that the charge is introduced into the bed nP and the final resulting product pp is removed, that, when the product pp no longer attains the required quality, the introduction of the charge into the bed np is stopped and simultaneously the charge is introduced into the bed np-1, the product obtained Pp-1 being introduced into the bed np, and then generally when the final product pp no longer attains the required quality, the introduction of the charge into the bed ni is stopped, at the same time the charge is introduced into the bed ni-1, the product obtained pi-1 being introduced into the bed ni, and so on until i has assumed all the whole values 1 from 1 to p.
  2. A process according to claim 1 characterised in that at least two catalytic beds are arranged successively and separately one above the other, the bed np being the lower and the bed n1 being the higher and the charge flowing in a downward flow through the bed or beds.
  3. A process according to one of the preceding claims characterised in that all the catalytic beds are arranged successively and separately in the same reactor, the charge being introduced at the beginning over the lowest catalytic bed (np) and flowing with a downward flow, the resulting product being removed in the bottom part of the reactor, and, when said product has a minimum performance threshold, the new upper catalyst bed is brought into service by stopping the introduction of charge above the previous bed used and introducing the charge above the fresh catalyst bed, the charge then flowing towards the bottom of the reactor by passing through the catalytic beds which are in service.
  4. A process according to one of the preceding claims characterised in that the hydrocarbon charge contains diolefins.
  5. A process according to one of the preceding claims characterised in that the charge is formed by gasoline produced from steam cracking or other cracking processes.
  6. A process according to one of the preceding claims characterised in that, the charge having been introduced in the last bed n1 and the final product Pp no longer being of the required quality, the temperature of the total mass is progressively increased in order to re-attain and maintain the required quality of the final product pp, that being effected until complete deactivation of the catalyst occurs.
EP93400164A 1992-01-28 1993-01-25 Selective hydrogenation process, particularly of steam cracking gasolines, with a catalyst in several sequentially used beds Expired - Lifetime EP0554151B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9200992 1992-01-28
FR9200992A FR2686617B1 (en) 1992-01-28 1992-01-28 PROCESS FOR SELECTIVE HYDROGENATION OF HYDROCARBON CHARGE WITH CATALYTIC LETS CARRIED OUT SUCCESSIVELY.

Publications (2)

Publication Number Publication Date
EP0554151A1 EP0554151A1 (en) 1993-08-04
EP0554151B1 true EP0554151B1 (en) 1996-07-10

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US (1) US5306852A (en)
EP (1) EP0554151B1 (en)
JP (1) JPH05247475A (en)
CN (1) CN1045950C (en)
DE (1) DE69303505T2 (en)
ES (1) ES2093370T3 (en)
FR (1) FR2686617B1 (en)
IN (1) IN181752B (en)

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Publication number Priority date Publication date Assignee Title
FR2720754B1 (en) * 1994-06-01 1996-07-26 Inst Francais Du Petrole Method and installation for the treatment by selective hydrogenation of a catalytic cracked gasoline.
FR2724390B1 (en) * 1994-09-08 1996-12-13 Inst Francais Du Petrole SELECTIVE HYDROGENATION OF HYDROCARBON CUTTINGS CONTAINING SINGLE AND UNSATURATED HYDROCARBONS
US5954950A (en) * 1995-09-07 1999-09-21 Institut Francais Du Petrole Intensive hydrofining of petroleum fractions
FR2743079B1 (en) * 1995-12-27 1998-02-06 Inst Francais Du Petrole PROCESS AND DEVICE FOR SELECTIVE HYDROGENATION BY CATALYTIC DISTILLATION INCLUDING A LIQUID-GAS UPWARD CO-CURRENT REACTION ZONE
US5847251A (en) 1996-02-12 1998-12-08 Catalytic Distillation Technologies Multibed transalkylator and process
EP0921179A1 (en) * 1997-12-05 1999-06-09 Fina Research S.A. Production of olefins
FR2970260B1 (en) * 2011-01-10 2014-07-25 IFP Energies Nouvelles METHOD FOR HYDROTREATING HEAVY HYDROCARBON LOADS WITH PERMUTABLE REACTORS INCLUDING AT LEAST ONE SHORT-CIRCUIT STEP OF A CATALYTIC BED
FR2970261B1 (en) * 2011-01-10 2013-05-03 IFP Energies Nouvelles METHOD FOR HYDROPROCESSING HYDROCARBON HEAVY LOADS WITH PERMUTABLE REACTORS INCLUDING AT LEAST ONE PROGRESSIVE PERMUTATION STEP
EP2865440A1 (en) * 2013-10-28 2015-04-29 Haldor Topsoe A/S Process and reactor for exothermal reaction
WO2017130081A1 (en) * 2016-01-27 2017-08-03 Sabic Global Technologies B.V. Processes and systems for increasing selectivity for light olefins in co2 hydrogenation

Family Cites Families (7)

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Publication number Priority date Publication date Assignee Title
FR1306238A (en) * 1961-10-19 1962-10-13 Shell Int Research Process for refining gasolines obtained by cracking and containing dienes
US3705204A (en) * 1967-05-18 1972-12-05 Nippon Oil Co Ltd Process for recovering conjugated diolefins selectively from a c5 fraction
US3926784A (en) * 1973-08-22 1975-12-16 Gulf Research Development Co Plural stage residue hydrodesulfurization process with hydrogen sulfide addition and removal
NL191763C (en) * 1979-09-26 1996-07-02 Shell Int Research Method of demetallizing a hydrocarbon oil.
US4560815A (en) * 1983-04-25 1985-12-24 The Babcock & Wilcox Company Automated catalyst regeneration in a reactor
US4704492A (en) * 1986-12-24 1987-11-03 Mobil Oil Corporation Selective hydrogenation of acetylenic impurities in crude butadiene
GB8702654D0 (en) * 1987-02-06 1987-03-11 Davy Mckee Ltd Process

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DE69303505T2 (en) 1996-11-21
CN1045950C (en) 1999-10-27
ES2093370T3 (en) 1996-12-16
IN181752B (en) 1998-09-12
US5306852A (en) 1994-04-26
EP0554151A1 (en) 1993-08-04
DE69303505D1 (en) 1996-08-14
JPH05247475A (en) 1993-09-24
FR2686617A1 (en) 1993-07-30
FR2686617B1 (en) 1994-03-18

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