EP0113283B1 - 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 PDF

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EP0113283B1
EP0113283B1 EP19830402494 EP83402494A EP0113283B1 EP 0113283 B1 EP0113283 B1 EP 0113283B1 EP 19830402494 EP19830402494 EP 19830402494 EP 83402494 A EP83402494 A EP 83402494A EP 0113283 B1 EP0113283 B1 EP 0113283B1
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Prior art keywords
catalyst
step
pore volume
nanometers
pores
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German (de)
French (fr)
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EP0113283A1 (en
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Alain Billon
Yves Jacquin
Jean-Pierre Peries
Hervé Toulhoat
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G45/00Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02Refining 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
    • C10G45/04Refining 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
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/107Atmospheric residues having a boiling point of at least about 538 °C

Description

  • 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, more easily transportable or processable fractions by the usual refining processes. Coal hydrogenation oils can also be processed.
  • 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 a normal boiling point above 520 ° C., into a stable hydrocarbon product, easily transportable, of low content of metals, sulfur and asphaltenes and having only a reduced content, for example less than 20% by weight, of constituents with a normal boiling point above 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. For example, crude oil from Boscan or Cerro Negro can contain 200 to 1000 ppm by weight, or more, of metals; these metals are mainly vanadium and nickel, with varying proportions of iron and other metals.
  • 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 (1) 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 (11), in HDS conditions, then on the inactive catalyst (1), under hydrovisbreaking conditions.
  • US-A-3,730,875 describes a process for converting asphaltenic hydrocarbon feedstocks containing sulfur and metals which comprises the following three successive steps:
    • a) catalytic hydrogenation,
    • b) non-catalytic thermal hydrocracking,
    • c) a catalytic hydrocracking of at least part of the product of step (b).
  • According to the very clear teaching of this document, for the process described to be effective it is essential that the catalyst of step (a) is a catalyst which does not adsorb asphaltenes and metals (column 3, lines 19 to 21).
  • EP-A-55 164 relates to alumina agglomerates of particular characteristics and a method of preparation of these agglomerates. This document further reveals that these agglomerates can be used as a support for the manufacture of catalysts which can be used in a very large number of reactions. Among the reactions for which this support can be used are hydrotreatments of petroleum products (page 11, lines 21 to 32).
  • The supports prepared according to the process described in this document can be microporous, macroporous or be of bimodal type, that is to say, comprising micropores and macropores. The majority of the supports described in the examples are of bimodal type comprising both macropores and micropores.
  • So there is room on the market for a truly continuous process, in which the hydrotreating catalyst can be used for several weeks or months without deactivation.
  • The invention therefore relates to a process for treating a heavy oil or a heavy oil fraction, containing asphaltenes, to convert them into lighter fractions, characterized by the following steps:
    • a) passing the charge, mixed with hydrogen, under hydrodemetallization conditions, over a catalyst containing alumina and at least one metal of at least one of groups V, VI and VIII (iron group), said catalyst consisting of juxtaposed agglomerates each formed from a plurality of needle-like plates, the plates of each agglomerate being oriented generally radially with respect to each other and with respect to the center of the agglomerate, said catalyst containing a major proportion of wedge-shaped mesopores,
    • b) the product of step (a) is subjected to hydroviscoreduction conditions, and
    • c) the product of step (b) is treated with hydrogen in contact with a catalyst containing alumina and at least one metal or metal compound chosen from the group which comprises molybdenum, tungsten, nickel, cobalt and iron.
  • According to a preferred variant, step (c) is implemented in two successive steps:
    • firstly in contact with a catalyst (C,) 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
      Figure imgb0001
      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; - then in contact with a catalyst (C 2 ) 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
      Figure imgb0002
      being between 0.2: 1 and 0.5: 1, preferably between 0.25: 1 and 0.35: 1. One of the metals in the numerator or denominator may be absent.
  • The weight ratio of catalyst C 2 to catalyst Ci is preferably from 1: 1 to 9: 1.
  • The catalyst of step (a) has been described in French patent application 82 10757 of June 17, 1982 and in patent application EP-A 98 764. The essential information is given below.
  • As a general rule, a large proportion, most often at least 50% of the acicular platelets, have a dimension along their axis of greatest development of between 0.05 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, most often at 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.
  • 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 catalyst used in the invention has a porous distribution preferably characterized as follows:
    • - 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.
  • The specific surface of this catalyst is between 50 and 250 m 2 / g and particularly preferably between 120 and 180 m 2 / g.
  • The scanning electron microscopy technique makes it possible to characterize unambiguously by micrographs a catalyst having the above structure. Figures 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 that are just described.
  • FIG. 6 presents a photomicrograph with a nominal magnification of 110,000 times of a bundle of needle-shaped 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.
  • On the other hand, FIGS. 7 to 10 show four microphotographs taken at the same respective magnifications as FIGS. 2 to 5 and with the same apparatus, on a sample of catalyst (catayleur B) prepared using bimodal alumina beads obtained by the process patented in France under the number 2 449 474: these photographs illustrate well the description which is given in this last patent, namely that the macroporosity results from the interparticle voids existing between microporous spheroidal particles, of which the particle size distribution and the compactness of the stacking determine the macroporous volume and the size of the macropores. In the photographs of FIGS. 2 to 5 and 7 to 10, 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 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.
  • The catalysts used in step (a) of the present process have excellent resistance to clogging of the pore plugs; this result can be explained as follows:
    • - The pores present in these catalysts, consisting mainly of the free spaces located between the radiating needle-like plates, are pores "at the 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 of diameters less than 10 nanometers, as in known catalysts, but they themselves constitute a mesoporosity offering a catalytically active surface.
  • 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: Use is made, as support, of alumina agglomerates in particles of the order of 0.1 to 10 millimeters or powder in particles of the order of 20 to 100 micrometers themselves having the above-mentioned sea urchin structure and having substantially the same characteristics as those of the catalyst of the invention, no. particularly with regard to the shapes and dimensions of the wafers and agglomerates, the specific surface and the porosity.
  • 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.
  • 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 unnecessary to list them here. We finish with optional drying and heat treatment at a temperature between 400 and 800 degrees centigrade.
  • To prepare the alumina agglomerates, it is possible to start with alumina or alumina containing other elements, for example sodium, rare earths or silica. An alumina containing 100 to 1000 parts per million by weight of silica is preferred. The procedure is preferably as follows:
    • 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.
  • 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 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.
  • 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.
  • Then, if necessary, the ripening, drying and / or calcination of the agglomerates.
  • 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 specific surface is between approximately 100 and approximately 350 m 2 / g, their total pore volume is between approximately 0.45 and approximately 1.5 c m 3 / 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.
  • Here, the term “acid making it possible to dissolve at least part of the alumina of the agglomerates” means any acid which, brought into contact with the active alumina agglomerates 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%.
  • 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 .
  • Here, the term “compound providing an anion capable of combining with the aluminum ions in solution” is understood to mean any compound capable of liberating an anion A (-n) capable of forming with the cations AI (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)., Ay 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%.
  • Use is preferably made of the compounds capable of releasing in solution the anions chosen from the group consisting of the nitrate, chloride, sulfate, perchlorate, chloroacetate, dichloracetate, trichloracetate, bromoacetate, dibromacetate anions, and the anions of general formula:
    Figure imgb0003
    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 operate 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.
  • 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.
  • According to a particularly preferred embodiment, 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.
  • Without limiting the method 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 the hydrothermal treatment results in 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.
  • 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.
  • 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. Activation is preferably carried out at a temperature between about 550 ° C and 950 ° C.
  • The resulting active alumina agglomerates have the following characteristics:
    • 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.
  • 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.
  • A specific surface area measured by the BET method of between approximately 80 and approximately 250 m 2 / g.
  • Mechanical strength between 2 and about 20 kg, measured by the grain-by-grain crushing method.
  • 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.
  • With regard to step (c) of the process, it has been specified above that the operation is preferably carried out using two successive beds of catalysts, named above (Ci) and (C 2 ).
  • The catalyst support (C,) preferably consists of an alumina of low acidity, that is to say having a heat of neutralization by adsorption of ammonia at 320 ° C 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 been autoclaved 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 born 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 cm 3 / g. Mention may be made, as supports meeting these characteristics of alumina y ex boehmite or it ex bayerite, or else supports of the alumina / magnesia or silica / magnesia type containing approximately 5 to 10% by weight of magnesia.
  • 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 charge or result from the passage of the latter.
    • - Step (a) is carried out at a temperature generally between 350 and 425 ° C, under a pressure of 40 to 200 bars, using an hourly flow rate of liquid charge of 0.2 to 2 m 3 / m 3 / h, the amount of hydrogen usually being 300 to 3000 Nm 3 / m 3 .
    • - Step (b) is carried out in the presence of hydrogen in an empty reaction space or containing a relatively inert material, at a temperature between 420 and 500 ° C under a pressure of 40 to 200 bars, the time of the charge stay being approximately 10 s to 15 min, and the quantity 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 amount of hydrogen usually being 500 to 3000 Nm 3 / m 3 , and the hourly charge rate liquid being from 0.2 to 2 m 3 / m 3 / h.
  • The invention is illustrated in Figure 11.
  • A mixture of heavy asphaltic 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 hydrogen supplied by line 6 to reactor 7 containing a first bed of catalyst 8 and a second bed of catalyst 9. The final product is drawn off through 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: (dl 5 ) 0.965, an API degree less than 15.1, an asphaltene content (determined with n-heptane) greater than 5% by weight, a metal content ( Ni + V) greater than 200 ppm by weight and a viscosity greater than 50 cSt (50 mm 2 / s) at 100 ° C.
  • Example
  • We process a Cerro Negro crude with the following characteristics:
    • d l 5 = 1 , 007
    • ° API = 9
    • Metals (Ni + V) = 500 ppm by weight
    • Asphaltenes (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
  • Passing this crude, supplemented with hydrogen, on a catalyst (A) containing, by weight:
    Figure imgb0004
  • 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, 3000, 10 000 and 20 000. The scales indicated on each photograph allow 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 the 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 needle-like plates can be measured in particular in FIG. 6, which is a photomicrograph taken at nominal magnification 110,000 with a scanning transmission electron microscope (S.T.E.M. VG HB5). The dark areas this time correspond to the catalytic material. The scale of this micrograph 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 intervals 1 therefore give an approximate measurement of the thickness of the wafers and the interval 2 a measurement of the width of the wafers, that is to say approximately 2 to 4 nanometers and 60 nanometers respectively, the wafers of FIG. 0.5 to 1 micrometer, which is in agreement with the measurable lengths in Figure 5 where we see these plates arranged in the agglomerates. The ratio of the average length to the average width is therefore approximately 8 to 16 and the ratio of the average length to the average thickness is approximately 120 to 480.
  • FIG. 1 shows in particular the cumulative porous distribution curve of the catalyst C. The diameter of the pores (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.
  • The passage of charge and hydrogen over the catalyst (A) presulfurized is carried out under the following conditions:
    • -temperature: 380 to 410 ° C
    • - pressure: 150 bars
    • - hourly liquid charge rate: 0.5 m 3 / m 3 / h
    • -H 2 quantity: 800 Nm 3 / m 3 of load.
  • The effluent is then subjected to step (b) of the process (hydroviscoreduction). The conditions are as follows:
    • -pressure: 150 bars
    • -temperature:
      • 460 ° C in the oven
      • 450 ° C in the maturation chamber
    • -time of residence:
      • 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)).
  • The hydroviscoreduction effluent is sent, with hydrogen, to a reactor comprising two successive beds of catalyst:
    • 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 Ni = 1.68. The support of this catalyst is an alumina of low acidity, having a heat of neutralization by adsorption of NH 3 of 20 joules / g; its specific surface is 140 m 2 / g, its pore volume being 0.48 c m3 / g.
  • This catalyst is a commercial catalyst sold by the French company PRO-CATALYSE under the name LD 145.
  • The second bed represents 80% by weight of the sum of the catalysts used; it consists of cobalt and molybdenum in a weight ratio
    Figure imgb0005
    = 0.25. 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 final liquid product obtained after these operations has the following characteristics:
    • Figure imgb0006
      = 0.885
    • ° API = 28.4
    • 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%.
  • 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)

1. A process for treating an asphaltene-containing heavy oil or heavy oil fraction to convert it to lighter fractions, characterized by the following steps of:
a) passing the charge, admixed with hydrogen, under hydrodemetallation conditions, over a catalyst containing alumina and at least one metal from at least one of groups V, VI and VIII (iron group), said catalyst consisting of juxtaposed conglomerates each formed of a plurality of acicular plates, the plates of each conglomerate being generally radially oriented with respect to one another and with respect to the center of the conglomerate, said catalyst comprising a major proportion of wedge-shaped mesopores;
b) subjecting the product from step (a) to hydrovisbreaking conditions; and
c) treating the product from step (b) with hydrogen in contact with a catalyst containing alumina and at least one metal or compound of a metal selected from the group comprising molybdenum, tungsten, nickel, cobalt and iron.
2. A process according to claim 1, wherein step (c) is conducted first in contact with a catalyst C1, then in contact with a catalyst Cz, each of these catalysts containing alumina, at least one molybdenum and/or tungsten compound and at least, one nickel and/or cobalt compound, the ratio by weight of the metals
Figure imgb0009
being from 0.8:1 to 3:1 for catalyst C, and from 0.2:1 to 0.5:1 for catalyst C2, the ratio by weight of catalyst C2 to catalyst C, being from 1:1 to 9:1, one of the metals at the numerator or at the denominator being optionally omitted.
3. A process according to one of claims 1 or 2, wherein the hydrovisbreaking conditions are:
- pressure: 40 to 200 bars
-temperature: 420to 550 °C
- hydrogen amount in proportion to the charge: 300 to 3000 Nm3/m3
- residence time: 10 seconds to 15 minutes.
4. A process according to any of claims 1 to 3, wherein the catalyst conglomerates of step (a) have an average size generally from 1 to 20 micrometers, the acicular plats having an average length generally from 0.05 to 5 micrometers, a ratio of their average length to their average width generally from 2 to 20 and a ratio of their average length to their average thickness generally from 1 to 5000.
5. A process according to any of claims 1 to 4, wherein the catalyst of step (a) has a specific surface from 50 to 250 m2/g, a total pore volume from 0.7 to 2.0 cm3/g and a pore distribution as follows:
-% of the total pore volume in pores of average diameter smaller than 10 nanometers: 0-10
- % of the total pore volume in pores of average diameter from 10 to 100 nanometers: 40-90
- % of the total pore volume in pores of average diameter from 100 to 500 nanometers: 5-60
- % of the total pore volume in pores of average diameter from 500 to 1000 nanometers: 5-50
- % of the total pore volume in pores of average diameter larger than 1000 nanometers: 5- 20.
6. A process according to any of claims 1 to 5 wherein the catalyst carrier of step (a) is alumina containing from 100 to 1000 ppm of silica.
7. A process according to any of claims 1 to 6, wherein the catalyst of step (a) contains from 0.5 to 40% by weight of at least one metal from at least one of group V, VI and VIII (iron group) expressed as oxides.
EP19830402494 1982-12-30 1983-12-21 Treatment of a heavy hydrocarbon oil or a heavy hydrocarbon oil fraction for their conversion into lighter fractions Expired EP0113283B1 (en)

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FR8222209A FR2538811B1 (en) 1982-12-30 1982-12-30
FR8222209 1982-12-30

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EP (1) EP0113283B1 (en)
JP (1) JPS59166589A (en)
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DE (1) DE3371535D1 (en)
FR (1) FR2538811B1 (en)
ZA (1) ZA8309686B (en)

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US8372267B2 (en) 2008-07-14 2013-02-12 Saudi Arabian Oil Company Process for the sequential hydroconversion and hydrodesulfurization of whole crude oil
US8491779B2 (en) 2009-06-22 2013-07-23 Saudi Arabian Oil Company Alternative process for treatment of heavy crudes in a coking refinery
US8632673B2 (en) 2007-11-28 2014-01-21 Saudi Arabian Oil Company Process for catalytic hydrotreating of sour crude oils
US9260671B2 (en) 2008-07-14 2016-02-16 Saudi Arabian Oil Company Process for the treatment of heavy oils using light hydrocarbon components as a diluent

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US8632673B2 (en) 2007-11-28 2014-01-21 Saudi Arabian Oil Company Process for catalytic hydrotreating of sour crude oils
US8372267B2 (en) 2008-07-14 2013-02-12 Saudi Arabian Oil Company Process for the sequential hydroconversion and hydrodesulfurization of whole crude oil
US9260671B2 (en) 2008-07-14 2016-02-16 Saudi Arabian Oil Company Process for the treatment of heavy oils using light hydrocarbon components as a diluent
US8491779B2 (en) 2009-06-22 2013-07-23 Saudi Arabian Oil Company Alternative process for treatment of heavy crudes in a coking refinery

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FR2538811A1 (en) 1984-07-06
FR2538811B1 (en) 1985-03-15
DE3371535D1 (en) 1987-06-19
CA1226842A (en) 1987-09-15
CA1226842A1 (en)
EP0113283A1 (en) 1984-07-11
US4511458A (en) 1985-04-16
ZA8309686B (en) 1985-08-28
JPS59166589A (en) 1984-09-19

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