EP0113283A1 - Treatment of a heavy hydrocarbon oil or a heavy hydrocarbon oil fraction for their conversion into lighter fractions - Google Patents
Treatment of a heavy hydrocarbon oil or a heavy hydrocarbon oil fraction for their conversion into lighter fractions Download PDFInfo
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- EP0113283A1 EP0113283A1 EP83402494A EP83402494A EP0113283A1 EP 0113283 A1 EP0113283 A1 EP 0113283A1 EP 83402494 A EP83402494 A EP 83402494A EP 83402494 A EP83402494 A EP 83402494A EP 0113283 A1 EP0113283 A1 EP 0113283A1
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- catalyst
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- alumina
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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
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
Definitions
- the invention relates to the treatment of heavy oils or heavy petroleum fractions, with a high asphaltene content, with the aim of converting them into lighter fractions, more easily transportable or treatable by the usual refining processes.
- Coal hydrogenation oils can also be processed.
- the invention solves the problem of the transformation of a viscous crude oil, non-transportable, rich in metals, sulfur and asphaltenes, and containing more than 50% of constituents with normal boiling point greater than 520 ° C., into a stable, easily transportable hydrocarbon product, of low content of metals, sulfur and asphaltenes and having only a reduced content, for example less than 20% by weight, of constituents with normal boiling point greater than 520 ° C. .
- the problem solved by the invention has long been the subject of work; the main difficulty to be overcome is that of deactivation of the catalysts by impurities, in particular metallic impurities, of the treated charges.
- impurities in particular metallic impurities
- crude oil from Boscan or Cerro Negro can contain 200 to 1,000 ppm by weight, or more, of metals; these metals are mainly vanadium and nickel, with varying proportions of iron and other metals.
- step (c) is implemented in two successive steps:
- a catalyst (C 1 ) containing alumina, at least one molybdenum and / or tungsten compound and at least one nickel and / or cobalt compound the weight ratio of the metals being fixed between 0.8: 1 and 3: 1 and preferably between 1: 1 and 2: 1;
- One of the metals in the numerator or denominator may be absent;
- One of the metals in the numerator or denominator may be absent.
- the weight ratio of catalyst C2 to catalyst C1 is preferably from 1: 1 to 9: 1.
- FIG. 1 makes it possible to compare the porous distribution curve of a catalyst (A) as used in step (a) of the invention and those corresponding to monomodal (C) or bimodal (B) catalysts produced according to prior art.
- the specific surface of this catalyst is between 50 and 250 m 2 / g and particularly preferably between 120 and 180 m 2 / g.
- FIGS. 2 to 5 show four micrographs at 300 times, 3000 times, 10,000 times and 20,000 times respectively of a catalyst used according to the invention (catalyst A) which illustrate the particular structure in juxtaposed sea urchins just to describe.
- FIG. 6 presents a photomicrograph at nominal magnification 110,000 times of a bundle of needle-like plates of catalyst A, which clearly illustrates the typical appearance of these plates.
- the intervals between the opposite arrows marked 1 mark the trace of platelets on the field and are an approximate measure of the thickness of these platelets.
- the interval between the opposite arrows marked 2 marks a plate parallel to the plane of the photograph and is a measure of the average width of this plate.
- the scale is 9 nanometers per millimeter and the dark parts correspond to the catalytic material.
- Figures 7 to 10 show four micrographs taken at the same respective magnifications as Figures 2 to 5 and with the same apparatus, on a sample of catalyst (catalyst B) prepared using bimodal alumina beads obtained by the process patented in France under number 2 449 474: these photographs illustrate the description given in this latter patent , namely that the macroporosity results from the interparticle voids existing between spheroidal microporous particles, whose particle size distribution and the compactness of the stack determine the macroporous volume and the size of the macropores.
- the dark areas correspond to the empty spaces of the structures of the catalysts, that is to say to the macroporosity, while the light parts correspond to the catalytic material.
- the distribution of the diameters of the macropores of catalyst B can be measured in the photographs and it corresponds well to that which is obtained by porosimetry with mercury and which is represented in FIG. 1.
- the comparison of the microphotographs clearly shows that the spheroidal particles microporous catalyst B do not have the sea urchin structure obtained for catalyst A used in step (a) of the invention.
- a catalyst which can be used for stage (a) of the invention can be prepared according to the following method, without limiting the invention to this particular method of preparation:
- Alumina agglomerates in particles of the order of 0.1 to 10 millimeters or in powdered particles in the order of 20 to 100 micrometers are themselves used as support, themselves having the above-mentioned sea urchin structure and responding substantially to the same characteristics than those of the catalyst of the invention, in particular as regards the shapes and dimensions of the wafers and agglomerates, the specific surface and the porosity.
- the catalytic metal or metals namely at least one metal or metal compound belonging to at least one of groups V, VI and VIII (iron group) of the classification periodic, more particularly at least one of the following metals: molybdenum, tungsten, iron, vanadium, cobalt and nickel.
- molybdenum + cobalt molybdenum + nickel, vanadium + nickel, tungsten + nickel.
- the aforementioned metals are most often introduced in the form of precursors such as oxides, acids, salts, organic complexes, and in amounts such that the catalyst contains from 0.5 to 40% and preferably from 1 to 20% by weight of these metals expressed as oxides. These precursors are well known and: it is therefore useless to list them here. We end with optional drying and heat treatment at a temperature between 400 and 800 degrees centigrade.
- the active alumina agglomerates used according to the present invention can be prepared from an active alumina powder having a poorly crystallized and / or amorphous structure, for example obtained according to the process described in French patent n ° 1 438,497.
- the active alumina used is generally obtained by rapid dehydration of aluminum hydroxides such as bayerite, hydrargillite or gibbsite, nordstrandite or aluminum oxyhydroxides such as boehmite and diaspore.
- the agglomeration of active alumina is carried out according to methods well known to those skilled in the art and, in particular, by pelleting, extrusion, bead shaping with a rotating bezel, etc.
- this agglomeration is carried out, as is well known to those skilled in the art, by adding blowing agents to the mixture to be agglomerated.
- blowing agents which can be used are in particular wood flour, charcoal, cellulose, starches, naphthalene and, in general, all the organic compounds capable of being eliminated by calcination.
- the active alumina agglomerates obtained generally have the following characteristics: their loss on ignition measured by calcination at 1000 ° C. is between approximately 1 and approximately 15%, their surface specific is between about 100 and about 350 m 2 / g, their total pore volume is between about 0.45 and about 1.5 cm3 / g
- the active alumina agglomerates are then treated in an aqueous medium consisting of a mixture of at least one acid making it possible to dissolve at least part of the alumina of the agglomerates and at least one compound providing an anion capable of forming combine with aluminum ions in solution.
- the acid must dissolve at least 0.5% and at most 15% by weight of alumina in the agglomerates. Its concentration in the aqueous treatment medium must be less than 20% by weight and preferably between 1% and 15 % .
- Use will preferably be made of strong acids such as nitric acid, hydrochloric acid, perchloric acid, sulfuric acid or weak acids used at a concentration such that their aqueous solution has a pH of less than about 4 .
- the term “compound providing an anion capable of combining with aluminum ions in solution” means any compound capable of liberating in an anion A (-n) capable of forming with the cations Al (3+) products in which the atomic ratio n (A / Al) is less than or equal to 3.
- a particular case of these compounds can be illustrated by the basic salts of general formula A12 (OH) xAy in which 0 ⁇ x ⁇ 6; ny ⁇ 6; n represents the number of charges of anion A.
- the concentration of this compound in the aqueous treatment medium must be less than 50% by weight and preferably between 3% and 30 % .
- the compounds capable of releasing in solution the anions chosen from the group consisting of the nitrate, chloride, sulphate, perchlorate, chloroacetate, dichloracetate, trichloroacetate, brichoacetate, bromoacetate, dibromacetate anions are preferably used, and the anions of general formula: in which R represents a radical taken from the group comprising H, CH 3 , C 2 H 5 , CH 3 CH 2 CH 2 , (CH 3 ) 2 CH.
- the compounds capable of liberating the anion A (-n) in solution can effect this liberation, either directly for example by dissociation, or indirectly for example by hydrolysis.
- the compounds can in particular be chosen from the group comprising: mineral or organic acids, anhydrides, organic or mineral salts, esters.
- mineral salts there may be mentioned the alkaline or alkaline-earth salts soluble in an aqueous medium, such as those of sodium, potassium, magnesium or calcium, ammonium salts, aluminum salts, earth salts rare.
- This treatment can be carried out either by dry impregnation of the agglomerates, or by immersion of the agglomerates in the aqueous solution consisting of the above-mentioned mixture of acid and of compound providing the desired anion.
- dry impregnation is intended to bring the alumina agglomerates into contact with a volume of solution less than or equal to the total pore volume of the agglomerates treated.
- mixtures of nitric and acetic acid or nitric and formic acid will be used as the aqueous medium.
- the agglomerates thus treated are subjected simultaneously or subsequently to a treatment at a temperature between approximately 80 and approximately 250 ° C. for a period of time between approximately 5 minutes and approximately 36 hours.
- This hydrothermal treatment does not cause any loss of alumina.
- the operation is preferably carried out at a temperature between 120 and 220 ° C. for a period of time between 15 minutes and 18 hours.
- This treatment constitutes a hydrothermal treatment of the active alumina agglomerates which realizes the transformation of at least part of these into boehmite.
- This hydrothermal treatment can be carried out either under saturated vapor pressure, or under a partial vapor pressure of water at least equal to 70% of the saturated vapor pressure corresponding to the treatment temperature.
- the concentration of the acid and of the compound in the treatment mixture and the hydrothermal treatment conditions used are such that there is no loss of alumina.
- the increase in porosity following the treatment is therefore due to an expansion of the agglomerates during the treatment and not to a loss of alumina.
- the agglomerates thus treated are then optionally dried at a temperature generally between approximately 100 and 200 ° C. for a period of time sufficient to remove the water which is not chemically bound.
- the agglomerates are then subjected to thermal activation at a temperature between about 500 ° C and about 1100 ° C for a period between about 15 minutes and 24 hours.
- Activation operations can be done in several stages. An activation will preferably be carried out at a temperature between about 550 ° C and 950 ° C.
- the aforementioned process for the preparation of alumina agglomerates makes it possible in particular and completely unexpectedly to modify the distribution of the pore volumes according to the pore size of the untreated agglomerates. It makes it possible in particular to increase the proportion of pores between 10 and 100 nanometers, to reduce the proportion of pores less than 10 nanometers and to decrease the proportion of pores greater than 500 nanometers by modifying little the proportion of pores between 100 and 500 nanometers.
- the alumina agglomerates thus obtained may have been thermally stabilized by rare earths, silica or alkaline earth metals.
- step (c) of the process it has been specified above that the operation is preferably carried out using two successive beds catalysts, named above (CI) and (C 2 ).
- the catalyst support (C 1 ) preferably consists of an alumina of low acidity, that is to say having a heat of neutralization by adsorption of ammonia at 320 ° C. of less than 40 joules (and preferably less than 30 joules) per gram of alumina, under an ammonia pressure of 0.4 bars.
- This alumina support has an area of 50 to 300 m 2 / g and preferably 40 to 150 m 2 / g, as well as a pore volume generally between 0.4 and 1.3 cm 3 / g .
- the aluminas which have undergone autoclaving under steam pressure can be cited.
- the catalyst (C 2 ) used in the second catalytic bed will preferably be incorporated on a support having a more acidic character than the support of the catalyst (C l ): its acidity, determined as above by adsorption of ammonia, will preferably be greater than 30 joules / g. Its surface is preferably between 150 and 350 m 2 / g, and its pore volume preferably between 0.4 and 1 cm3 / g. Mention may be made, as supports meeting these characteristics of alumina y ex boehmite or n ex bayerite, or else supports of the alumina / magnesia or silica / magnesia type containing approximately 5 to 10% by weight of magnesia.
- steps (a) and (c) of the process are conventional. These catalysts work mainly, during operation, in sulfurized form; their sulfurization may be prior to the treatment of the load or result from the passage of the latter.
- active metals for example Mo, W, Ni, Co, Fe
- a mixture of asphaltic heavy oil and hydrogen is sent by line 1 to the catalytic hydrodemetallization reactor 2, then by line 3 to the water reduction reduction reactor 4.
- the effluent is sent by line 5 preferably in the presence a supply of hvdroqene supplied by line 6 to the line in the presence of a supply of hydrogen supplied by line 6 to the reactor 7 containing a first bed of catalyst 8 and a second bed of catalyst 9.
- the final product is drawn off by line 10.
- the fillers which can be treated according to the invention are, for example, crude oils, vacuum residues, atmospheric residues, shale oil or oil sands oils or asphalts. Oils most often have a density greater than: ( ) 0.965, an API degree less than 15.1, an asphaltenes content (determined with n-heptane) greater than 5% by weight, a metal content (Ni + V) greater than 200 ppm by weight and a higher viscosity at 50 cSt (50 mm 2 / s) at 100 ° C.
- FIG. 2 to 5 show photomicrographs of catalyst A taken using a JEOL brand scanning electron microscope, model JSM 35 CF, at respective magnifications 300, 3,000, 10,000 and 20,000.
- the scales indicated on each photograph measure the dimensions of observable details.
- the dark parts correspond to the porosity, while the light parts correspond to the catalytic material.
- catalyst A does indeed have the "sea urchin" structure according to the invention, namely a juxtaposition of agglomerates having for the most part an average dimension of 3.5 micrometers, each agglomerate being formed of elongated needle-like plates, generally assembled radially with respect to the center of the agglomerates.
- the dimensions of the acicular plates are measurable in particular in FIG.
- FIG. 1 shows in particular the cumulative porous distribution curve of catalyst A.
- This catalyst is a commercial catalyst sold by the French company PRO-CATALYSE under the name LD 145.
- Its support is of the alumina y type, having a specific surface of 210 m 2 / g, the pore volume being 0.52 cm 3 / g; this support has a heat of neutralization by adsorption of NH 3 of 40 joules / g.
- This catalyst is a commercial catalyst sold by the French company PRO-CATALYSE under the name HR 306.
- the weight ratio of catalyst from the 2nd bed to the 1st bed is therefore 4.
- the temperature in the reactor is between 370 and 400 ° C, the pressure being 140 bars.
- the hourly flow rate of liquid charge is 0.5 m 3 / m 3 / h, the quantity of hydrogen relative to the charge is 1,200 Nm 3 / m 3 .
- the process therefore made it possible to transform a heavy, viscous crude, non-transportable, with a high content of impurities, into a stable synthetic crude, easily transportable, with a low content of impurities.
- the service life of the catalysts is exceptional, given the nature of the charge. The test was stopped after 2300 hours, while the activity of the catalyst in step (a) still represented 50 % of the initial activity. The retention power of this catalyst is exceptional (130 g of fixed metals per 100 g of fresh catalyst).
Abstract
Conversion d'un pétrole lourd ou d'une fraction lourde de pétrole, contenant des asphaltènes, en fractions plus légères. Le procédé comprend 3 étapes : une hydrodémétallisation catalytique (2), une hydroviscoréduction (4) et un hydrotraitement catalytique (7). On obtient une huile d'hydrocarbures plus légère, purifiée, stabilisée et aisément transportable.Conversion of heavy petroleum or a heavy petroleum fraction, containing asphaltenes, to lighter fractions. The process comprises 3 stages: a catalytic hydrodemetallization (2), a hydroviscoreduction (4) and a catalytic hydrotreatment (7). A lighter, purified, stabilized and easily transportable hydrocarbon oil is obtained.
Description
L'invention concerne le traitement de pétroles lourds ou de fractions lourdes de pétrole, à forte teneur en asphaltènes, dans le but de les convertir en fractions moins lourdes, plus aisément transportables ou traitables par les procédés usuels de raffinage. Les huiles d'hydrogè- nation du charbon peuvent aussi être traitées.The invention relates to the treatment of heavy oils or heavy petroleum fractions, with a high asphaltene content, with the aim of converting them into lighter fractions, more easily transportable or treatable by the usual refining processes. Coal hydrogenation oils can also be processed.
Plus particulièrement, l'invention résoud le problème de la transformation d'un pétrole brut visqueux, non transportable, riche en métaux, soufre et asphaltènes, et contenant plus de 50 % de constituants de point d'ébullition normal supérieur à 520°C, en un produit hydrocarboné stable, aisément transportable, de faible teneur en métaux, soufre et asphaltènes et n'ayant qu'une teneur réduite, par exemple moins de 20 % en poids, de constituants de point d'ébullition normal supérieur à 520°C.More particularly, the invention solves the problem of the transformation of a viscous crude oil, non-transportable, rich in metals, sulfur and asphaltenes, and containing more than 50% of constituents with normal boiling point greater than 520 ° C., into a stable, easily transportable hydrocarbon product, of low content of metals, sulfur and asphaltenes and having only a reduced content, for example less than 20% by weight, of constituents with normal boiling point greater than 520 ° C. .
Le problème résolu par l'invention a longtemps fait l'objet de travaux; la principale difficulté à vaincre est celle de la désactivation des catalyseurs par les impuretés, notamment les impuretés métalliques, des charges traitées. C'est ainsi, par exemple, qu'un pétrole brut de Boscan ou de Cerro Negro peut renfermer de 200 à 1 000 ppm en poids, ou plus, de métaux ; ces métaux sont principalement le vanadium et le nickel, avec des proportions variables de fer et d'autres métaux.The problem solved by the invention has long been the subject of work; the main difficulty to be overcome is that of deactivation of the catalysts by impurities, in particular metallic impurities, of the treated charges. For example, crude oil from Boscan or Cerro Negro can contain 200 to 1,000 ppm by weight, or more, of metals; these metals are mainly vanadium and nickel, with varying proportions of iron and other metals.
La désactivation des catalyseurs d'hydrotraitement est illustrée par le brevet US 4.017.380 qui propose de remédier à cette difficulté par emploi d'un procédé cyclique ; une unité d'hydrodésulfuration (HDS) catalytique(I) précède une unité de visbreaking (II) contenant un catalyseur d'HDS désactivé ; dès que le catalyseur d'hydrodésulfuration actif (I) est désactivé, on inverse les opérations après avoir pris soin de remplacer le catalyseur (II) par du catalyseur frais : la charge passe alors sur le catalyseur actif d'HDS (II), dans des conditions d'HDS, puis sur le catalyseur inactif (I) , dans des conditions d'hydrovis- breaking.The deactivation of hydrotreatment catalysts is illustrated by US Pat. No. 4,017,380 which proposes to remedy this difficulty by using a cyclic process; a catalytic hydrodesulfurization unit (HDS) (I) precedes a visbreaking unit (II) containing a deactivated HDS catalyst; as soon as the active hydrodesulfurization catalyst (I) is deactivated, the operations are reversed after taking care to replace the catalyst (II) with fresh catalyst: the charge then passes over the active HDS catalyst (II), in HDS conditions, then on the inactive catalyst (I), under hydrovisbreaking conditions.
Il y a donc place sur le marché pour un procédé réellement continu, dans lequel le catalyseur d'hydrotraitement peut être utilisé pendant plusieurs semaines ou plusieurs mois sans désactivation.There is therefore room on the market for a truly continuous process, in which the hydrotreating catalyst can be used for several weeks or months without deactivation.
Le procédé de l'invention comprend les étapes essentielles suivantes :
- a) Dans une première étape, on fait passer la charge d'hydrocarbures, mélangée à de l'hydrogène, sur un catalyseur renfermant de l'alumine et au moins un métal ou composé de métal de l'un au moins des groupes V, VI et VIII (groupe du fer), ledit catalyseur étant caractérisé en ce qu'il est constitué d'une pluralité d'agglomérats juxtaposés formés chacun d'une pluralité de plaquettes aciculaires, les plaquettes de chaque agglomérat étant orientées généralement radialement les unes par rapport aux autres et par rapport au centre de l'agglomérat.
- b) Dans une seconde étape, le produit de l'étape (a) est soumis à des conditions d'hydroviscoréduction.
- c) Dans une troisième étape, le produit de l'étape (b) est soumis à un traitement par l'hydrogène, au contact d'un catalyseur renfermant de l'alumine et au moins un métal ou composé de métal choisi dans le groupe : molybdène, tungstène, nickel, cobalt et fer.
- a) In a first step, the charge of hydrocarbons, mixed with hydrogen, is passed over a catalyst containing alumina and at least one metal or compound of metal from at least one of the groups V, VI and VIII (iron group), said catalyst being characterized in that it consists of a plurality of juxtaposed agglomerates each formed of a plurality of needle-like plates, the plates of each agglomerate being oriented generally radially by one compared to others and to the center of the agglomeration.
- b) In a second stage, the product of stage (a) is subjected to hydroviscoreduction conditions.
- c) In a third step, the product of step (b) is subjected to a treatment with hydrogen, in contact with a catalyst containing alumina and at least one metal or metal compound chosen from the group : molybdenum, tungsten, nickel, cobalt and iron.
Selon une variante préférée, l'étape (c) est mise en oeuvre en deux étapes successives :According to a preferred variant, step (c) is implemented in two successive steps:
- d'abord au contact d'un catalyseur (C1) contenant de l'alumine, au moins un composé de molybdène et/ou tungstène et au moins un composé de nickel et/ou cobalt, le rapport pondéral des métaux
Le rapport en poids du catalyseur C2 au catalyseur C1 est de préférence de 1 : 1 à 9 : 1.The weight ratio of catalyst C2 to catalyst C1 is preferably from 1: 1 to 9: 1.
Le catalyseur de l'étape (a) a été décrit dans la demande de brevet français 82 10757 du 17 juin 1982 dont la description est incorporée ici par voie de référence. Les informations essentielles sont reprises ci-après :
- En règle générale, une large proportion, le plus souvent au moins 50 % des plaquettes aciculaires, ont une dimension suivant leur axe de plus grand développement comprise entre 0,05 et 5 micromètres et de préférence entre 0,1 et 2 micromètres, un rapport de cette dimension à leur largeur moyenne compris entre 2 et 20, et de préférence entre 5 et 15, un rapport de cette dimension à leur épaisseur moyenne compris entre 1 et 5000, et de préférence entre 10 et 200. Une large proportion, le plus souvent au moins 50 % des agglomérats de plaquettes aciculaires constituent une collection de particules pseudo-sphériques de taille moyenne comprise entre 1 et 20 micromètres, de préférence entre 2 et 10 micromètres. Des images très adéquates pour représenter une telle structure sont par exemple un tas de bogues épineuses de chataignes, ou encore un tas d'oursins de mer.
- As a general rule, a large proportion, most often at least 50% of acicular platelets, have a dimension along their axis of greatest development of between 0.05 and 5 micrometers and preferably between 0.1 and 2 micrometers, a ratio of this dimension at their average width between 2 and 20, and preferably between 5 and 15, a ratio of this dimension to their average thickness between 1 and 5000, and preferably between 10 and 200. A large proportion, the most often at least 50% of the acicular platelet agglomerates constitute a collection of pseudo-spherical particles of average size between 1 and 20 micrometers, preferably between 2 and 10 micrometers. Very suitable images to represent such a structure are for example a bunch of thorny chestnut bugs, or a bunch of sea urchins.
La figure 1 permet de comparer la courbe de répartition poreuse d'un catalyseur (A) tel qu'utilisé à l'étape (a) de l'invention et celles correspondant à des catalyseurs monomodaux (C) ou bimodaux (B) réalisés selon l'art antérieur.FIG. 1 makes it possible to compare the porous distribution curve of a catalyst (A) as used in step (a) of the invention and those corresponding to monomodal (C) or bimodal (B) catalysts produced according to prior art.
Le catalyseur utilisé dans l'invention a une distribution poreuse caractérisée de préférence comme suit :
- - Volume poreux total : 0,7 à 2,0 cm3/g, de préférence 0,90 à 1,30 cm3/g.
- - % du volume poreux total en pores de diamètre moyen inférieur à 10 nanomètres : 0 - 10.
- - % du volume poreux total en pores de diamètre moyen compris entre 10 et 100 nanomètres : 40 - 90.
- - % du volume poreux total en pores de diamètre moyen compris entre 100 et 500 nanomètres : 5 - 60.
- - % du volume poreux total en pores de diamètre moyen compris entre 500 et 1000 nanomètres : 5 - 50.
- - % du volume poreux total en pores de diamètre moyen supérieur à 1000 nanomètres : 5 - 20.
- - Total pore volume: 0.7 to 2.0 cm 3 / g, preferably 0.90 to 1.30 cm 3 / g .
- -% of the total pore volume in pores with an average diameter of less than 10 nanometers: 0 - 10.
- -% of the total pore volume in pores with an average diameter between 10 and 100 nanometers: 40 - 90.
- -% of the total pore volume in pores with an average diameter between 100 and 500 nanometers: 5 - 60.
- -% of the total pore volume in pores with an average diameter between 500 and 1000 nanometers: 5 - 50.
- -% of the total pore volume in pores with an average diameter greater than 1000 nanometers: 5 - 20.
La surface spécifique de ce catalyseur est comprise entre 50 et 250 m2/g et de manière particulièrement préférée entre 120 et 180 m2/g.The specific surface of this catalyst is between 50 and 250 m 2 / g and particularly preferably between 120 and 180 m 2 / g.
La technique de microscopie électronique à balayage permet de caractériser sans ambiguité par des microphotographies un catalyseur possédant la structure ci-dessus. Les figures 2 à 5 présentent quatre microphotographies aux grossissements 300 fois, 3000 fois, 10000 fois et 20 000 fois respectivement d'un catalyseur utilisé selon l'invention (catalyseur A) qui illustrent bien la structure particulière en oursins juxtaposés que l'on vient de décrire.The scanning electron microscopy technique makes it possible to characterize unambiguously by micrographs a catalyst having the above structure. FIGS. 2 to 5 show four micrographs at 300 times, 3000 times, 10,000 times and 20,000 times respectively of a catalyst used according to the invention (catalyst A) which illustrate the particular structure in juxtaposed sea urchins just to describe.
La figure 6 présente une microphotographie au grossissement nominal 110 000 fois d'un faisceau de plaquettes aciculaires du catalyseur A, qui illustre bien l'allure typique de ces plaquettes. Les intervalles entre les flèches opposées marquées 1 repèrent la trace de plaquettes sur champ et sont une mesure approximative de l'épaisseur de ces plaquettes. L'intervalle entre les flèches opposées marquées 2 repère une plaquette parallèle au plan de la photographie et est une mesure de la largeur moyenne de cette plaquette. Sur la figure 6, l'échelle est de 9 nanomètres pour un millimètre et les parties foncées correspondent à la matière catalytique.FIG. 6 presents a photomicrograph at nominal magnification 110,000 times of a bundle of needle-like plates of catalyst A, which clearly illustrates the typical appearance of these plates. The intervals between the opposite arrows marked 1 mark the trace of platelets on the field and are an approximate measure of the thickness of these platelets. The interval between the opposite arrows marked 2 marks a plate parallel to the plane of the photograph and is a measure of the average width of this plate. In Figure 6, the scale is 9 nanometers per millimeter and the dark parts correspond to the catalytic material.
En revanche, les figures 7 à 10 présentent quatre microphotographies prises aux mêmes grossissements respectifs que les figures 2 à 5 et avec le même appareil, sur un échantillon de catalyseur (catalyseur B) préparé en utilisant des billes d'alumine bimodales obtenues par le procédé breveté en France sous le numéro 2 449 474 : ces photographies illustrent bien la description qui est donnée dans ce dernier brevet, à savoir que la macroporosité résulte des vides interparticulaires existant entre des particules microporeuses sphéroidales, dont la répartition granulométrique et la compacité de l'empilement déterminent le volume macroporeux et la taille des macropores. Sur les photographies des figures 2 à 5 et 7 à 10, les plages foncées correspondent aux espaces vides des structures des catalyseurs, c'est à dire à la macroporosité, tandis que les parties claires correspondent à la matière catalytique. La répartition des diamètres des macropores du catalyseur B peut être mesurée sur les photographies et elle correspond bien à celle que l'on obtient par porosimétrie au mercure et qui est représentée figure 1. La comparaison des microphotographies fait bien appa- raitre que les particules sphéroidales microporeuses du catalyseur B n'ont pas la structure en oursin obtenue pour le catalyseur A utilisé dans l'étape (a) de l'invention.In contrast, Figures 7 to 10 show four micrographs taken at the same respective magnifications as Figures 2 to 5 and with the same apparatus, on a sample of catalyst (catalyst B) prepared using bimodal alumina beads obtained by the process patented in France under
Les catalyseurs utilisés dans l'étape (a) du présent procédé ont une excellente résistance au colmatage des bouches de pores ; ce résultat peut être expliqué comme suit :
- - Les pores présents dans ces catalyseurs, constitués en majorité par les espaces libres situés entre les plaquettes aciculaires rayonnantes, sont des pores "en coins" et donc de diamètre continument variable.
- - Ces pores rayonnants ne sont pas nécessairement linéaires en direction.
- - Ces pores rayonnants ne sont pas des canaux d'accès à des micropores de diamètres inférieurs à 10 nanomètres, comme dans les catalyseurs connus, mais ils constituent eux-mêmes une mésoporosité offrant une surface catalytiquement active.
- - The pores present in these catalysts, consisting mainly of the free spaces located between the radiating needle-like plates, are pores "in corners" and therefore of continuously variable diameter.
- - These radiating pores are not necessarily linear in direction.
- - These radiating pores are not access channels to micropores with diameters less than 10 nanometers, as in known catalysts, but they themselves constitute a mesoporosity offering a catalytically active surface.
Un catalyseur utilisable pour l'étape (a) de l'invention peut être préparé suivant la méthode suivante, sans limiter l'invention à cette méthode particulière de préparation :A catalyst which can be used for stage (a) of the invention can be prepared according to the following method, without limiting the invention to this particular method of preparation:
On utilise comme support des agglomérés d'alumine en particules de l'ordre de 0,1 à 10 millimètres ou en poudre en particules de l'ordre de 20 à 100 micromètres ayant eux-mêmes la structure en oursin précitée et répondant sensiblement aux mêmes caractéristiques que celles du catalyseur de l'invention, notamment en ce qui concerne les formes et les dimensions des plaquettes et des agglomérats, la surface spécifique et la porosité.Alumina agglomerates in particles of the order of 0.1 to 10 millimeters or in powdered particles in the order of 20 to 100 micrometers are themselves used as support, themselves having the above-mentioned sea urchin structure and responding substantially to the same characteristics than those of the catalyst of the invention, in particular as regards the shapes and dimensions of the wafers and agglomerates, the specific surface and the porosity.
Sur ces agglomérés, on dépose, par toute méthode connue, le ou les métaux catalytiques, à savoir au moins un métal ou composé de métal appartenant à l'un au moins des groupes V, VI et VIII (groupe du fer) de la classification périodique, plus particulièrement l'un au moins des métaux suivants : molybdène, tungstène, fer, vanadium, cobalt et nickel. Des associations préférées sont molybdène + cobalt, molybdène + nickel, vanadium + nickel, tungstène + nickel.On these agglomerates, using any known method, the catalytic metal or metals, namely at least one metal or metal compound belonging to at least one of groups V, VI and VIII (iron group) of the classification periodic, more particularly at least one of the following metals: molybdenum, tungsten, iron, vanadium, cobalt and nickel. Preferred combinations are molybdenum + cobalt, molybdenum + nickel, vanadium + nickel, tungsten + nickel.
Les métaux précités sont le plus souvent introduits sous forme de précurseurs tels que oxydes, acides, sels, complexes organiques, et en quantités telles que le catalyseur renferme de 0,5 à 40 %et de préférence de 1 à 20 % en poids de ces métaux exprimés en oxydes. Ces précurseurs sont bien connus et:il est donc inutile d'en donner une liste ici. On termine par un séchage éventuel et un traitement thermique à une température comprise entre 400 et 800 degrés centigrades.The aforementioned metals are most often introduced in the form of precursors such as oxides, acids, salts, organic complexes, and in amounts such that the catalyst contains from 0.5 to 40% and preferably from 1 to 20% by weight of these metals expressed as oxides. These precursors are well known and: it is therefore useless to list them here. We end with optional drying and heat treatment at a temperature between 400 and 800 degrees centigrade.
Pour préparer les agglomérés d'alumine, on peut partir d'alumine ou d'alumine renfermant d'autres éléments, par exemple du sodium, des terres rares ou de la silice. On préfère une alumine renfermant de 100 à 1 000 parties par million en poids de silice. On opère de préférence comme suit :
- a) On traite des agglomérés d'alumine dans un milieu aqueux constitué d'un mélange d'au moins un acide permettant de dissoudre au moins une partie de l'alumine des agglomérés et d'au moins un composé apportant un anion capable de se combiner avec les ions aluminium en solution, ce dernier composé étant un individu chimique distinct de l'acide précité.
- b) On soumet simultanément ou subséquemment les agglomérés ainsi traités à un traitement à une température comprise entre environ 80 degrés C et environ 250 degrés C pendant une période comprise entre environ quelques minutes et environ 36 heures.
- c) On sèche éventuellement les agglomérés et on les soumet à une activation thermique à une température comprise entre environ 500°C et
environ 1 100°C.
- a) Alumina agglomerates are treated in an aqueous medium consisting of a mixture of at least one acid making it possible to dissolve at least part of the alumina of the agglomerates and at least one compound providing an anion capable of combine with aluminum ions in solution, the latter compound being a chemical individual distinct from the aforementioned acid.
- b) The agglomerates thus treated are subjected simultaneously or subsequently to a treatment at a temperature between about 80 degrees C and about 250 degrees C for a period between about a few minutes and about 36 hours.
- c) The agglomerates are optionally dried and subjected to thermal activation at a temperature between approximately 500 ° C. and approximately 1100 ° C.
Les agglomérés d'alumine active mis en oeuvre selon la présente invention peuvent être préparés à partir d'une poudre d'alumine active présentant une structure mal cristallisée et/ou amorphe, par exemple obtenue selon le procédé décrit dans le brevet français n° 1 438 497.The active alumina agglomerates used according to the present invention can be prepared from an active alumina powder having a poorly crystallized and / or amorphous structure, for example obtained according to the process described in French patent n ° 1 438,497.
L'alumine active mise en oeuvre est généralement obtenue par déshydratation rapide des hydroxydes d'aluminium tels que la bayerite, l'hy- drargillite ou gibbsite, la nordstrandite ou les oxyhydroxydes d'aluminium tels que la boehmite et le diaspore.The active alumina used is generally obtained by rapid dehydration of aluminum hydroxides such as bayerite, hydrargillite or gibbsite, nordstrandite or aluminum oxyhydroxides such as boehmite and diaspore.
L'agglomération de l'alumine active est réalisée selon les méthodes bien connues de l'homme de l'art et, en particulier, par pastillage, extrusion, mise en forme de billes au drageoir tournant, etc.The agglomeration of active alumina is carried out according to methods well known to those skilled in the art and, in particular, by pelleting, extrusion, bead shaping with a rotating bezel, etc.
D'une manière préférée, cette agglomération est effectuée, ainsi qu'il est bien connu de l'homme de l'art, en ajoutant des agents porogènes au mélange à agglomérer. Les agents porogènes que l'on peut utiliser sont notamment la farine de bois, le charbon de bois, la cellulose, les amidons, le naphtalène et, d'une manière générale, tous les composés organiques susceptibles d'être éliminés par calcination.Preferably, this agglomeration is carried out, as is well known to those skilled in the art, by adding blowing agents to the mixture to be agglomerated. The blowing agents which can be used are in particular wood flour, charcoal, cellulose, starches, naphthalene and, in general, all the organic compounds capable of being eliminated by calcination.
On opère ensuite, le cas échéant, le mûrissement, le séchage et/ou la calcination des agglomérés.Then, if necessary, the ripening, drying and / or calcination of the agglomerates.
Les agglomérés d'alumine active obtenus présentent généralement les caractéristiques suivantes : leur perte au feu mesurée par calcination à 1 000°C est comprise entre environ 1 et environ 15 %, leur surface spécifique est comprise entre environ 100 et environ 350 m2/g, leur volume poreux total est compris entre environ 0,45 et environ 1,5 cm3/gThe active alumina agglomerates obtained generally have the following characteristics: their loss on ignition measured by calcination at 1000 ° C. is between approximately 1 and approximately 15%, their surface specific is between about 100 and about 350 m 2 / g, their total pore volume is between about 0.45 and about 1.5 cm3 / g
Les agglomérés d'alumine active sont ensuite traités dans un milieu aqueux constitué d'un mélange d'au moins un acide permettant de dissoudre au moins une partie de l'alumine des agglomérés et d'au moins un composé apportant un anion capable de se combiner avec les ions aluminium en solution.The active alumina agglomerates are then treated in an aqueous medium consisting of a mixture of at least one acid making it possible to dissolve at least part of the alumina of the agglomerates and at least one compound providing an anion capable of forming combine with aluminum ions in solution.
Au sens de l'invention, on entend par acide permettant de dissoudre au moins une partie de l'alumine des agglomérés tout acide qui, mis en contact avec les agglomérés d'alumine active définis ci-dessus, réalise la mise en solution d'au moins une partie des ions aluminium. L'acide doit dissoudre au moins 0,5 % et au plus 15 % en poids d'alumine des agglomérés. Sa concentration dans le milieu aqueux de traitement doit être inférieure à 20 % en poids et de préférence comprise entre 1 % et 15 %.Within the meaning of the invention, the term “acid making it possible to dissolve at least a portion of the alumina of the agglomerates any acid which, brought into contact with the agglomerates of active alumina defined above, achieves the dissolution of at least part of the aluminum ions. The acid must dissolve at least 0.5% and at most 15% by weight of alumina in the agglomerates. Its concentration in the aqueous treatment medium must be less than 20% by weight and preferably between 1% and 15 % .
On utilisera de préférence les acides forts tels que l'acide nitrique, l'acide chlorhydrique, l'acide perchlorique, l'acide sulfurique ou des acides faibles mis en oeuvre à une concentration telle que leur solution aqueuse présente un pH inférieur à environ 4.Use will preferably be made of strong acids such as nitric acid, hydrochloric acid, perchloric acid, sulfuric acid or weak acids used at a concentration such that their aqueous solution has a pH of less than about 4 .
Au sens de l'invention, on entend par composé apportant un anion capable de se combiner avec les ions aluminium en solution, tout composé capable de libérer en solution un anion A(-n) susceptible de former avec les cations Al(3+) des produits dans lesquels le rapport atomique n(A/Al) est inférieur ou égal à 3. Un cas particulier de ces composés peut être illustré par les sels basiques de formule générale A12(OH) xAy dans laquelle 0 < x < 6 ; ny < 6 ; n représente le nombre de charges de l'anion A.Within the meaning of the invention, the term “compound providing an anion capable of combining with aluminum ions in solution” means any compound capable of liberating in an anion A (-n) capable of forming with the cations Al (3+) products in which the atomic ratio n (A / Al) is less than or equal to 3. A particular case of these compounds can be illustrated by the basic salts of general formula A12 (OH) xAy in which 0 <x <6; ny <6; n represents the number of charges of anion A.
La concentration de ce composé dans le milieu aqueux de traitement doit être inférieure à 50 % en poids et de préférence comprise entre 3 % et 30 %.The concentration of this compound in the aqueous treatment medium must be less than 50% by weight and preferably between 3% and 30 % .
On utilise de préférence les composés capables de libérer en solution les anions choisis parmi le groupe constitué par les anions nitrate, chlorure, sulfate, perchlorate, chloroacétate, dichloracétate, trichlo- racétate, bromoacétate, dibromacétate, et les anions de formule générale :
Les composés capables de libérer en solution l'anion A(-n) peuvent opérer cette libération, soit directement par exemple par dissociation, soit indirectement par exemple par hydrolyse. Les composés peuvent notamment être choisis parmi le groupe comportant : les acides minéraux ou organiques, les anhydrides, les sels organiques ou minéraux, les esters. Parmi les sels minéraux, on peut citer les sels alcalins ou alcalino-terreux solubles en milieu aqueux, comme ceux du sodium, de potassium, de magnésium ou de calcium, les sels d'ammonium, les sels d'aluminium, les sels de terres rares.The compounds capable of liberating the anion A (-n) in solution can effect this liberation, either directly for example by dissociation, or indirectly for example by hydrolysis. The compounds can in particular be chosen from the group comprising: mineral or organic acids, anhydrides, organic or mineral salts, esters. Among the mineral salts, there may be mentioned the alkaline or alkaline-earth salts soluble in an aqueous medium, such as those of sodium, potassium, magnesium or calcium, ammonium salts, aluminum salts, earth salts rare.
Ce traitement peut être effectué soit par imprégnation à sec des agglomérés, soit par immersion des agglomérés dans la solution aqueuse constituée du mélange précité d'acide et de composé apportant l'anion désiré. Par imprégnation à sec, on entend mise en contact des agglomérés d'alumine avec un volume de solution inférieur ou égal au volume poreux total des agglomérés traités.This treatment can be carried out either by dry impregnation of the agglomerates, or by immersion of the agglomerates in the aqueous solution consisting of the above-mentioned mixture of acid and of compound providing the desired anion. By dry impregnation is intended to bring the alumina agglomerates into contact with a volume of solution less than or equal to the total pore volume of the agglomerates treated.
Selon un mode particulièrement préféré de mise en oeuvre de l'invention, on utilisera comme milieu aqueux des mélanges d'acide nitrique et acétique ou d'acide nitrique et formique.According to a particularly preferred embodiment of the invention, mixtures of nitric and acetic acid or nitric and formic acid will be used as the aqueous medium.
On soumet simultanément ou subséquemment les agglomérés ainsi traités à un traitement à une température comprise entre environ 80 et environ 250°C pendant une période de temps comprise entre environ 5 minutes et environ 36 heures.The agglomerates thus treated are subjected simultaneously or subsequently to a treatment at a temperature between approximately 80 and approximately 250 ° C. for a period of time between approximately 5 minutes and approximately 36 hours.
Ce traitement hydrothermique n'entraîne aucune perte d'alumine.This hydrothermal treatment does not cause any loss of alumina.
On opère de préférence à une température comprise entre 120 et 220°C pendant une période de temps comprise entre 15 minutes et 18 heures.The operation is preferably carried out at a temperature between 120 and 220 ° C. for a period of time between 15 minutes and 18 hours.
Ce traitement constitue un traitement hydrothermal des agglomérés d'alumine active qui réalise la transformation d'au moins une partie de ceux-ci en boehmite. Ce traitement hydrothermal peut être réalisé soit sous pression de vapeur saturante, soit sous une pression partielle de vapeur d'eau au moins égale à 70 % de la pression de vapeur saturante correspondant à la température de traitement.This treatment constitutes a hydrothermal treatment of the active alumina agglomerates which realizes the transformation of at least part of these into boehmite. This hydrothermal treatment can be carried out either under saturated vapor pressure, or under a partial vapor pressure of water at least equal to 70% of the saturated vapor pressure corresponding to the treatment temperature.
Sans limiter la présente invention à la théorie, on peut penser que l'association d'un acide qui permet la dissolution d'au moins une partie de l'alumine et d'un anion qui permet la formation des produits décrits ci-dessus lors du traitement hydrothermal entraîne l'obtention d'une boehmite particulière, précurseur des plaquettes aciculaires de l'invention, dont la croissance procède radialement à partir de germes de cristallisation.Without limiting the present invention to theory, it may be thought that the combination of an acid which allows the dissolution of at least part of the alumina and an anion which allows the formation of the products described above during hydrothermal treatment leads to the production of a particular boehmite, precursor of the needle-like platelets of the invention, the growth of which proceeds radially from germs of crystallization.
De plus, la concentration de l'acide et du composé dans le mélange de traitement et les conditions de traitement hydrothermal mises en oeuvre sont telles qu'il n'y a pas de perte d'alumine. L'augmentation de la porosité à la suite du traitement est donc due à une expansion des agglomérés au cours du traitement et non à une perte d'alumine.In addition, the concentration of the acid and of the compound in the treatment mixture and the hydrothermal treatment conditions used are such that there is no loss of alumina. The increase in porosity following the treatment is therefore due to an expansion of the agglomerates during the treatment and not to a loss of alumina.
Les agglomérés ainsi traités sont ensuite éventuellement séchés à une température généralement comprise entre environ 100 et 200°C pendant une période de temps suffisante pour enlever l'eau qui n'est pas chimiquement liée. Les agglomérés sont ensuite soumis à une activation thermique à une température comprise entre environ 500°C et environ 1 100°C pendant une période comprise entre environ 15 minutes et 24 heures.The agglomerates thus treated are then optionally dried at a temperature generally between approximately 100 and 200 ° C. for a period of time sufficient to remove the water which is not chemically bound. The agglomerates are then subjected to thermal activation at a temperature between about 500 ° C and about 1100 ° C for a period between about 15 minutes and 24 hours.
Les opérations d'activation peuvent se faire en plusieurs étapes. On opérera de préférence une activation à une température comprise entre environ 550 °C et 950°C.Activation operations can be done in several stages. An activation will preferably be carried out at a temperature between about 550 ° C and 950 ° C.
Les agglomérés d'alumine active résultants présentent les caractéristiques suivantes :
- Une densité de remplissage tassé comprise entre environ 0,36 et 0,75 g/cm 3.
- Un volume poreux total (VPT) compris
entre 0,7 etenviron 2,0 cm3/g.
- A packed filling density of between about 0.36 and 0.75 g / cm 3 .
- A total pore volume (VPT) of between 0.7 and about 2.0 cm 3 / g.
Une répartition des volumes poreux suivant la taille des pores conforme aux valeurs énoncées plus haut, concernant le catalyseur utilisé dans la première étape du procédé de l'invention, au facteur correctif près traduisant l'alourdissement dû au dépôt des métaux.A distribution of the pore volumes according to the size of the pores in accordance with the values stated above, concerning the catalyst used in the first step of the process of the invention, except for the corrective factor reflecting the weighting due to the deposition of metals.
Une surface spécifique mesurée par la méthode B.E.T. comprise entre environ 80 et environ 250 m2/g.A specific surface area measured by the BET method of between approximately 80 and approximately 250 m 2 / g.
Une solidité mécanique comprise entre 2 et environ 20 kg, mesurée par la méthode d'écrasement grain par grain.Mechanical strength between 2 and about 20 kg, measured by the grain-by-grain crushing method.
Le procédé précité de préparation d'agglomérés d'alumine permet notamment et de façon totalement inattendue de modifier la répartition des volumes poreux suivant la taille des pores des agglomérés non traités. Il permet notamment d'augmenter la proportion des pores compris entre 10 et 100 nanomètres, de réduire la proportion des pores inférieurs à 10 nanomètres et de diminuer la proportion des pores supérieurs à 500 nanomètres en modifiant peu la proportion des pores compris entre 100 et 500 nanomètres.The aforementioned process for the preparation of alumina agglomerates makes it possible in particular and completely unexpectedly to modify the distribution of the pore volumes according to the pore size of the untreated agglomerates. It makes it possible in particular to increase the proportion of pores between 10 and 100 nanometers, to reduce the proportion of pores less than 10 nanometers and to decrease the proportion of pores greater than 500 nanometers by modifying little the proportion of pores between 100 and 500 nanometers.
Les agglomérés d'alumine ainsi obtenus peuvent avoir été thermiquement stabilisés par les terres rares, la silice ou les métaux alcalino-terreux.The alumina agglomerates thus obtained may have been thermally stabilized by rare earths, silica or alkaline earth metals.
En ce qui concerne l'étape (c) du procédé, il a été précisé ci-dessus que l'on opérait préférentiellement en utilisant deux lits successifs de catalyseurs, nommés plus haut (CI) et (C2).With regard to step (c) of the process, it has been specified above that the operation is preferably carried out using two successive beds catalysts, named above (CI) and (C 2 ).
Le support du catalyseur (C1) est constitué de préférence par une alumine de faible acidité, c'est à dire présentant une chaleur de neutralisation par adsorption d'ammoniac à 320°C inférieure à 40 joules (et préférentiellement inférieure à 30 joules) par gramme d'alumine, sous une pression d'ammoniac de 0,4 bars. Ce support d'alumine présente une surface de 50 à 300 m2/g et, de préférence, de 40 à 150 m2/g, ainsi qu'un volume poreux généralement compris entre 0,4 et 1,3 cm3/g. On peut citer comme exemple de ce type de support les alumines ayant subi un autoclavage sous pression de vapeur d'eau.The catalyst support (C 1 ) preferably consists of an alumina of low acidity, that is to say having a heat of neutralization by adsorption of ammonia at 320 ° C. of less than 40 joules (and preferably less than 30 joules) per gram of alumina, under an ammonia pressure of 0.4 bars. This alumina support has an area of 50 to 300 m 2 / g and preferably 40 to 150 m 2 / g, as well as a pore volume generally between 0.4 and 1.3 cm 3 / g . As an example of this type of support, the aluminas which have undergone autoclaving under steam pressure can be cited.
Le catalyseur (C2) utilisé dans le deuxième lit catalytique sera de préférence incorporé sur un support présentant un caractère plus acide que le support du catalyseur (Cl) : son acidité, déterminée comme ci-dessus par adsorption d'ammoniac, sera préférentiellement supérieure à 30 joules/g. Sa surface est de préférence comprise entre 150 et 350 m2/g, et son volume poreux de préférence compris entre 0,4 et 1 cm3/g. On peut citer comme supports répondant à ces caractéristiques de l'alumine y ex boehmite ou n ex bayerite, ou encore des supports de type alumine/magnésie ou silice/magnésie contenant environ de 5 à 10 % en poids de magnésie.The catalyst (C 2 ) used in the second catalytic bed will preferably be incorporated on a support having a more acidic character than the support of the catalyst (C l ): its acidity, determined as above by adsorption of ammonia, will preferably be greater than 30 joules / g. Its surface is preferably between 150 and 350 m 2 / g, and its pore volume preferably between 0.4 and 1 cm3 / g. Mention may be made, as supports meeting these characteristics of alumina y ex boehmite or n ex bayerite, or else supports of the alumina / magnesia or silica / magnesia type containing approximately 5 to 10% by weight of magnesia.
Les techniques d'incorporation des métaux actifs (par exemple Mo, W, Ni, Co, Fe) présents aux étapes (a) et (c) du procédé sont conventionnelles. Ces catalyseurs fonctionnent principalement, en cours d'opération, sous forme sulfurée ; leur sulfuration peut être préalable au traitement de la charge ou résulter du passage de cette dernière.The techniques for incorporating active metals (for example Mo, W, Ni, Co, Fe) present in steps (a) and (c) of the process are conventional. These catalysts work mainly, during operation, in sulfurized form; their sulfurization may be prior to the treatment of the load or result from the passage of the latter.
- L'étape (a) est mise en oeuvre à une température généralement comprise entre 350 et 425°C, sous une pression de 40 à 200 bars, en utilisant un débit horaire de charge liquide de 0,2 à 2 m3/m3/h, la quantité d'hydrogène étant habituellement de 300 à 3 000 Nm3/m3.
- - L'étape (b) est mise en oeuvre en présence d'hydrogène dans un espace de réaction vide ou contenant un matériau relativement inerte, à une température comprise entre 420 et 500°C sous une pression de 40 à 200 bars, le temps de séjour de la charge étant d'environ 10 s à 15min, et la quantité d'hydrogène généralement comprise entre 300
et 3 000 Nm3/m3. - - L'étape (c) est mise en oeuvre entre 300 et 425°C, sous une pression de 30 à 200 bars, la quantité d'hydrogène étant habituellement de 500 à 3 000 Nm3/m3, et le débit horaire de charge liquide étant de 0,2 à 2 m3/m3/h.
- - Step (b) is carried out in the presence of hydrogen in an empty reaction space or containing a relatively inert material, a temperature between 420 and 500 ° C under a pressure of 40 to 200 bars, the charge residence time being about 10 s to 15 min, and the amount of hydrogen generally between 300 and 3000 Nm 3 / m 3 .
- - Step (c) is carried out between 300 and 425 ° C, under a pressure of 30 to 200 bars, the quantity of hydrogen usually being 500 to 3,000 Nm3 / m 3 , and the hourly charge rate liquid being from 0.2 to 2 m 3 / m 3 / h.
L'invention est illustrée par la figure 11.The invention is illustrated in Figure 11.
Un mélange d'huile lourde asphaltique et d'hydrogène est envoyé par la ligne 1 au réacteur d'hydrodémétallation catalytique 2, puis par la ligne 3 au réacteur d'hydroviscoréduction 4. L'effluent est envoyé par la liqne 5 de préférence en présence d'un appport d'hvdroqène fourni par la liqne 6 la ligne en présence d'un apport d'hydrogène fourni par la ligne 6 au réacteur 7 contenant un premier lit de catalyseur 8 et un second lit de catalyseur 9. Le produit final est soutiré par la ligne 10.A mixture of asphaltic heavy oil and hydrogen is sent by
Les charges qui peuvent être traitées selon l'invention sont, par exemple, les pétroles bruts, les résidus sous vide, les résidus atmosphériques, les huiles de schistes ou de sables bitumineux ou les asphaltes. Les huiles ont le plus souvent une densité supérieure à : (
On traite un brut de Cerro Negro présentant les caractéristiques suivantes :
Asphaltènes (extraits à l'heptane) = 10,5 % en poids Soufre = 3,7 % en poids % distillant au dessus de 520°C = 58 % en poids viscosité = 249 cSt (249 mm2/s) à 100°CAsphaltenes (heptane extract) = 10.5% by weight Sulfur = 3.7% by weight % distilling above 520 ° C = 58% by weight viscosity = 249 cSt (249 mm 2 / s) at 100 ° C
On fait passer ce brut, additionné d'hydrogène, sur un catalyseur (A) renfermant, en poids :
Les figures 2 à 5 présentent des microphotographies du catalyseur A effectuées au moyen d'un microscope électronique à balayage de marque JEOL, modèle JSM 35 CF, aux grandissements respectifs 300, 3 000, 10 000 et 20 000. Les échelles indiquées sur chaque photographie permettent de mesurer les dimensions des détails observables. Les parties sombres correspondent à la porosité, tandis que les parties claires correspondent à la matière catalytique. On peut voir que le catalyseur A possède bien la structure "en oursins" selon l'invention, à savoir une juxtaposition d'agglomérats ayant en majorité une dimension moyenne de 3,5 micromètres, chaque agglomérat étant formé de plaquettes allongées aciculaires, assemblées généralement radialement par rapport au centre des agglomérats. Les dimensions des plaquettes aciculaires sont mesurables en particulier sur la figure 6, qui est une microphotographie prise au grossissement nominal 110 000 avec un microscope électronique à transmission à balayage (S.T.E.M. VG HB5). Les plages sombres correspondent cette fois à la matière catalytique. L'échelle de cette microphotographie est de 9 nanomètres pour un millimètre. Les intervalles délimités par des flèches opposées repérées 1 et 2 correspondent respectivement aux traces de plaquettes aciculaires disposées perpendiculairement et parallèlement au plan de l'image. Les intervalles 1 donnent donc une mesure approximative de l'épaisseur des plaquettes et l'intervalle 2 une mesure de largeur de plaquette, soit respectivement environ 2 à 4 nanomètres et 60 nanomètres, les plaquettes de la figure 6 ont une longueur de l'ordre de 0,5 à 1 micromètre, ce qui est en accord avec les longueurs mesurables sur la figure 5 où l'on voit ces plaquettes disposées dans les agglomérats. Le rapport de la longueur moyenne à la largeur moyenne est donc d'environ 8 à 16 et le rapport de la longueur moyenne à l'épaisseur moyenne est d'environ 120 à 480.Figures 2 to 5 show photomicrographs of catalyst A taken using a JEOL brand scanning electron microscope, model JSM 35 CF, at respective magnifications 300, 3,000, 10,000 and 20,000. The scales indicated on each photograph measure the dimensions of observable details. The dark parts correspond to the porosity, while the light parts correspond to the catalytic material. It can be seen that catalyst A does indeed have the "sea urchin" structure according to the invention, namely a juxtaposition of agglomerates having for the most part an average dimension of 3.5 micrometers, each agglomerate being formed of elongated needle-like plates, generally assembled radially with respect to the center of the agglomerates. The dimensions of the acicular plates are measurable in particular in FIG. 6, which is a photomicrograph taken at nominal magnification 110,000 with a scanning transmission electron microscope (STEM VG HB5). The dark areas this time correspond to the catalytic material. The scale of this photomicrograph is 9 nanometers per millimeter. The intervals delimited by opposite arrows marked 1 and 2 correspond respectively to the traces of needle-like plates arranged perpendicularly and parallel to the plane of the image. The
La figure 1 présente notamment la courbe de répartition poreuse cumulée du catalyseur A. Le diamètre des pores (D), exprimé en nanomètres, figure en abscisses et le volume poreux cumulé (V), exprimé en cm3/g, en ordonnées. On peut constater que la répartition est conforme à la définition de l'invention et en particulier qu'elle ne possède pas de point d'inflexion intermédiaire bien marqué.FIG. 1 shows in particular the cumulative porous distribution curve of catalyst A. The pore diameter (D), expressed in nanometers, is shown on the abscissa and the cumulative pore volume (V), expressed in cm 3 / g, on the ordinate. It can be seen that the distribution conforms to the definition of the invention and in particular that it does not have a well marked intermediate point of inflection.
Le passage de la charge et de l'hydrogène sur le catalyseur (A) présul- furé se fait dans les conditions suivantes :
- - température : 380 à 410°C
- - pression : 150 bars
- - débit horaire de charge liquide : 0,5 m3/m3/h
- - quantité d'H2 : 800 Nm3/m3 de charge.
- - temperature: 380 to 410 ° C
- - pressure: 150 bars
- - hourly liquid charge rate: 0.5 m 3 / m 3 / h
- - quantity of H 2 : 800 Nm 3 / m 3 of charge.
L'effluent est ensuite soumis à l'étape (b) du procédé (hydroviscoréduction). Les conditions sont les suivantes :
- - pression : 150 bars
- - température : 460°C dans le four 450°C dans la chambre de maturation
- - temps de résidence : 10 s dans le four 8 min dans la chambre de maturation
- - quantité d'H2 par rapport à la charge : 800 Nm3/m3 (provenant de l'étape (a)).
- - pressure: 150 bars
- - temperature: 460 ° C in the oven 450 ° C in the ripening chamber
- - residence time: 10 s in the
oven 8 min in the maturation chamber - - amount of H 2 relative to the feed: 800 Nm 3 / m 3 (from step (a)).
L'effluent d'hydroviscoréduction est envoyé, avec de l'hydrogène, dans un réacteur comprenant deux lits successifs de catalyseur :
- Le premier lit représente 20 % en poids de la somme des deux catalyseurs utilisés ; il est constitué par du nickel et du molybdène dans un rapport pondéral
- The first bed represents 20% by weight of the sum of the two catalysts used; it consists of nickel and molybdenum in a weight ratio
Ce catalyseur est un catalyseur commercial vendu par la Société française PRO-CATALYSE sous la dénomination LD 145.This catalyst is a commercial catalyst sold by the French company PRO-CATALYSE under the name LD 145.
Le deuxième lit représente 80 % en poids de la somme des catalyseurs utilisés ; il est constitué par du cobalt et du molybdène dans un rapport pondéral
Ce catalyseur est un catalyseur commercial vendu par la Société française PRO-CATALYSE sous la dénomination HR 306.This catalyst is a commercial catalyst sold by the French company PRO-CATALYSE under the name HR 306.
Le rapport pondéral de catalyseur du 2e lit au 1er lit est donc de 4.The weight ratio of catalyst from the 2nd bed to the 1st bed is therefore 4.
La température est comprise, dans le réacteur, entre 370 et 400°C, la pression étant de 140 bars. Le débit horaire de charge liquide est de 0,5 m3/m3/h, la quantité d'hydrogène par rapport à la charge est de 1 200 Nm3/m3. The temperature in the reactor is between 370 and 400 ° C, the pressure being 140 bars. The hourly flow rate of liquid charge is 0.5 m 3 / m 3 / h, the quantity of hydrogen relative to the charge is 1,200 Nm 3 / m 3 .
Le produit liquide final obtenu après ces opérations présente les caractéristiques suivantes :
- Teneur en métaux (Ni + V) < 10 ppm en poids
- Teneur en asphaltènes (extraits à l'heptane) : 1,5 % en poids
- Teneur en soufre : 0,3 % en poids
- % distillant au-dessus de 520° C = 12 % en poids
- Viscosité : 2,5 cSt (2,5 mm2/s) à 100°C 30 cSt (30 mm2/s) à 20°C
- Rendement pondéral de l'effluent liquide par rapport au brut d'origine : 94 %.
- Metal content (Ni + V) <10 ppm by weight
- Asphaltenes content (heptane extracts): 1.5% by weight
- Sulfur content: 0.3% by weight
- % distilling above 520 ° C = 12% by weight
- Viscosity: 2.5 cSt (2.5 mm 2 / s) at 100 ° C 30 cSt (30 mm 2 / s) at 20 ° C
- Weight yield of the liquid effluent compared to the original crude oil: 94 %.
Le procédé a donc permis de transformer un brut lourd, visqueux, non transportable, à forte teneur en impuretés, en un brut synthétique stable, aisément transportable, à faible teneur en impuretés. La durée de vie des catalyseurs est exceptionnelle, compte tenu de la nature de la charge. L'essai a été interrompu après 2 300 heures, alors que l'activité du catalyseur de l'étape (a) représentait encore 50 % de l'activité initiale. Le pouvoir de rétention de ce catalyseur est exceptionnel (130 g de métaux fixés pour 100 g de catalyseur frais) .The process therefore made it possible to transform a heavy, viscous crude, non-transportable, with a high content of impurities, into a stable synthetic crude, easily transportable, with a low content of impurities. The service life of the catalysts is exceptional, given the nature of the charge. The test was stopped after 2300 hours, while the activity of the catalyst in step (a) still represented 50 % of the initial activity. The retention power of this catalyst is exceptional (130 g of fixed metals per 100 g of fresh catalyst).
Claims (7)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8222209A FR2538811A1 (en) | 1982-12-30 | 1982-12-30 | PROCESS FOR TREATING HEAVY OIL OR HEAVY OIL FRACTION TO CONVERT THEM TO LOWER FRACTIONS |
FR8222209 | 1982-12-30 |
Publications (2)
Publication Number | Publication Date |
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EP0113283A1 true EP0113283A1 (en) | 1984-07-11 |
EP0113283B1 EP0113283B1 (en) | 1987-05-13 |
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ID=9280767
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP83402494A Expired EP0113283B1 (en) | 1982-12-30 | 1983-12-21 | Treatment of a heavy hydrocarbon oil or a heavy hydrocarbon oil fraction for their conversion into lighter fractions |
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Country | Link |
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US (1) | US4511458A (en) |
EP (1) | EP0113283B1 (en) |
JP (1) | JPS59166589A (en) |
CA (1) | CA1226842A (en) |
DE (1) | DE3371535D1 (en) |
FR (1) | FR2538811A1 (en) |
ZA (1) | ZA839686B (en) |
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EP0219080A2 (en) * | 1985-10-15 | 1987-04-22 | Hoechst Aktiengesellschaft | Water soluble disazo compounds, process for their preparation and their use as dyestuffs |
EP0537500A2 (en) * | 1991-10-09 | 1993-04-21 | Idemitsu Kosan Company Limited | A method of treatment of heavy hydrocarbon oil |
EP0584369A1 (en) * | 1992-02-21 | 1994-03-02 | Idemitsu Kosan Company Limited | Process for hydrotreating heavy hydrocarbon oil |
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US4626340A (en) * | 1985-09-26 | 1986-12-02 | Intevep, S.A. | Process for the conversion of heavy hydrocarbon feedstocks characterized by high molecular weight, low reactivity and high metal contents |
US5024750A (en) * | 1989-12-26 | 1991-06-18 | Phillips Petroleum Company | Process for converting heavy hydrocarbon oil |
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EP2234710A2 (en) | 2007-11-28 | 2010-10-06 | Saudi Arabian Oil Company | Process for catalytic hydrotreating of sour crude oils |
WO2010009077A2 (en) | 2008-07-14 | 2010-01-21 | Saudi Arabian Oil Company | Process for the treatment of heavy oils using light hydrocarbon components as a diluent |
US8372267B2 (en) | 2008-07-14 | 2013-02-12 | Saudi Arabian Oil Company | Process for the sequential hydroconversion and hydrodesulfurization of whole crude oil |
US8480881B2 (en) * | 2009-06-11 | 2013-07-09 | Board Of Regents, The University Of Texas System | Synthesis of acidic silica to upgrade heavy feeds |
BRPI1012764A2 (en) | 2009-06-22 | 2019-07-09 | Aramco Services Co | Alternative process for treating heavy crude oils in a coking refinery. |
CN111100678A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Method for hydrotreating residual oil by using up-flow reactor |
CN111097547A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Residual oil hydrotreating catalyst carrier, catalyst and preparation method thereof |
CN111100676A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Catalyst grading method and application thereof in residual oil hydrotreating method |
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- 1983-12-21 DE DE8383402494T patent/DE3371535D1/en not_active Expired
- 1983-12-29 ZA ZA839686A patent/ZA839686B/en unknown
- 1983-12-29 JP JP58252368A patent/JPS59166589A/en active Pending
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- 1983-12-30 US US06/567,209 patent/US4511458A/en not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
---|---|
US4511458A (en) | 1985-04-16 |
EP0113283B1 (en) | 1987-05-13 |
ZA839686B (en) | 1985-08-28 |
DE3371535D1 (en) | 1987-06-19 |
CA1226842A (en) | 1987-09-15 |
FR2538811A1 (en) | 1984-07-06 |
JPS59166589A (en) | 1984-09-19 |
FR2538811B1 (en) | 1985-03-15 |
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