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(11) | EP 0 021 495 B1 |
| (12) | EUROPEAN PATENT SPECIFICATION |
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Process for the catalytic hydrodesulphurization of a residual fraction of a hydrocarbon oil Verfahren zur katalytischen, hydrierenden Entschwefelung einer Rückstandsfraktion eines Kohlenwasserstofföls Procédé d'hydrodésulfuration catalytique d'une fraction résiduelle d'une huile hydrocarbonée |
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| Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). |
[0001] The invention relates to a process for the catalytic hydrodesulphurization of a residual fraction of a hydrocarbon oil with a high metal content.
[0002] When refining hydrocarbon oils, such as mineral oils and in particular petroleum, the light products are usually first removed by distillation at atmospheric pressure, subsequently heavier fractions are separated off by means of vacuum distillation and the remaining residue (the short residue) is deasphalted, in which process deasphalted vacuum residue of a mineral oil (referred to as DAO below) and asphalt are obtained. The heavier fractions obtained in the vacuum distillation (also known as vacuum distillate fractions) and the residual fractions, in particular DAO, can be used inter alia as heavy fuel or as feedstock for catalytic cracking. In order to discharge the smallest possible quantity of sulphur compounds to the atmosphere in the combustion of heavy fuel, it is necessary that the sulphur content of oils to be used as heavy fuel is as low as possible. If DAO and/or vacuum distillate fractions are used as feed for a catalytic cracking reaction the metal content and the tendency toward coke deposition of the feed to be used must be as low as possible in order to prevent rapid deactivation of the cracking catalyst.
[0003] In order to meet the requirements laid down regarding sulphur and metal content, both vacuum distillate fractions and residual fractions (by which are meant fractions which have remained behind as residue in vacuum distillation or have been obtained from such residue, for example short residue, DAO, asphalt) must generally be desulphurized, and at least part of the metals, which occur in a larger quantity in the residual fractions than in the vacuum distillate fractions, must be removed. These metals consist for the greater part of nickel and vanadium, which may be present in substantial quantities in hydrocarbon oils, such as mineral oils.
[0004] In this application, by a "high metal content" is meant a metal content which is so high that the usual catalysts for hydrodesulphurization are not resistant thereto.
[0005] The catalysts usually used for catalytic desulphurization are not resistant to quantities of metal in the feed which are higher than about 20 parts by weight per million (ppm), since in the case of larger quantities of metal an unacceptable pressure drop across the catalyst occurs after a relatively short time. For this reason a residual fraction, for example DAO, having a metal content which is substantially higher than 20 ppm cannot be desulphurized by means of these catalysts in an economically justified manner. The metal content of the residual fraction can be so high that even after blending the whole quantity of residual fraction to be desulphurized with available vacuum distillate fractions (the latter fractions containing only small quantities of metal) the metal content of the blend is still too high for desulphurization by means of the usual catalysts. It is of course possible to demetallize the residual fraction before desulphurization by means of a suitable catalyst, but this requires the construction and operation of extra plants, which is unattractive in many cases.
[0006] The invention provides a process by which, with the application of catalytic hydrodesulphurization only and without the life of the desulphurization catalyst being reduced unacceptably, it is still possible to obtain products having desired low sulphur and low metal contents.
[0007] The invention therefore relates to a process for the catalytic hydrodesulphurization of a residual fraction of a hydrocarbon oil with a high metal content, characterized in that a blend of part of said residual fraction and at least part of a distillate fraction of a hydrocarbon oil with a lower metal content is passed over a catalyst in the presence of hydrogen, and the remainder of the residual fraction is supplied to the catalyst at one or more downstream points.
[0008] As hydrocarbon oils may be mentioned mineral oils, such as shale oil, oil recovered from tar sands, and in particular petroleum.
[0009] As distillate fraction of a hydrocarbon oil, such as of a mineral oil, use is very suitably made of a vacuum distillate fraction, in particular a "flashed distillate", that is a high-boiling oil which is obtained from petroleum by vacuum flash distillation. The boiling range of a flashed distillate generally lies, entirely or largely, between 300 and 550°C, and the metal content is generally less than 5 ppm, in particular less than 2 ppm.
[0010] As a residual fraction a deasphalted vacuum residue (DAO) is very suitably used; the metal content thereof is generally considerably higher, for example, 20-60 ppm.
[0011] By blending at least part of the distillate fraction with part of the residual fraction a blend can be obtained which has a much lower metal content than the residual fraction. For said blend use is preferably made of all the flashed distillate becoming available in the vacuum distillation for the preparation of the relevant residual fraction, such a quantity of residual fraction being incorporated into the blend that metal content thereof is so low that the blend can be hydrodesulphurized without objection by means of a usual desulphurization catalyst. The quantities of metal which the blend may contain are of course dependent on the "metal sensitivity" (an indication of the quantity of metal which may still be present in the feed without giving rise to problems) of the specific desulphurization catalyst one intends to use. Use is preferably made of a desulphurization catalyst which with the application of feeds containing up to 20 ppm of metal is still satisfactory in operation.
[0012] The remainder of the residual fraction is supplied at one or more points downstream of the catalyst. Since said points of the catalyst are also passed by the blend which has been supplied as feed at the beginning of the process and which is already completely or partly desulphurized and demetallized, the residual fraction is blended therewith and the blend thus obtained again has a metal content which is not detrimental to the desulphurization catalyst. If the residual fraction has a very high metal content and the metal content of the blend obtained during the addition of the entire remainder of the residual fraction were to become too high at one downstream point, the remainder of the residual fraction is supplied to the catalyst in various portions, each portion further downstream than the previous one.
[0013] If desired, part of the distillate fraction can also be supplied at one or more downstream points. Very suitably various catalyst beds are used in series. They are preferably arranged in several reactors.
[0014] It is possible to use as catalyst hydrodesulphurization catalysts known as such, such as catalysts consisting of a carrier on which one or more metals of groups VIB and VIII of the periodic system (and/or compounds of said metals such as sulphides or oxides thereof) have been deposited. Catalysts which contain cobalt and/or nickel together with molybdenum and/or tungsten are very suitable. Silica, alumina and silica-alumina are very suitable as carriers. Preference is given to catalysts containing 2-6% by weight of nickel (calculated as oxide) and 8-16% by weight of molybdenum calculated as oxide (percentages based on carrier) on an alumina carrier having a surface area of 100-300 m2/g and a pore volume 0.3-0.7 ccm/g, since catalysts of this type have a relatively low metal sensitivity, that is to say that feeds with a relatively high metal content (up to about 20 ppm) can be used without the occurrence of undesirable effects. The catalysts are preferably sulphided before use.
[0015] The reaction conditions during the hydrodesulphurization are the usual ones. Suitable are temperatures of 300-450°C, a total pressure of 45-150 bar, a hydrogen partial pressure of 30-120 bar, a space velocity of 0.1-8.0 kg of feed per kg of catalyst per hour and a quantity of hydrogen of 250-2000 nl per litre of feed. Very suitable are temperatures of 330-390°C, a total pressure of 70-95 bar, a hydrogen partial pressure of 50-80 bar, a space velocity of 0.2-0.4 kg of feed per kg of catalyst per hour, and a quantity of hydrogen of 400-900 nl per litre of feed.
[0016] The oil to be desulphurized and hydrogen may be passed countercurrently over the catalyst, but it is preferred to pass the oil to be desulphurized and the hydrogen over the catalyst in the same, preferably downward, direction, in which case the hydrogen can be completely or partly dissolved in the oil.
[0017] The invention will now be illustrated with reference to the Figure. This Figure is diagrammatical and auxiliaries which are immaterial to the nature of the invention, such as pumps, valves, heat exchangers and furnaces, have been omitted.
[0018] Through a line 1 residual fraction is supplied, part of which is blended through a line 2 with distillate fraction supplied through a line 3. To the blend thus obtained hydrogen is supplied through a line 4 and the blend of oil and hydrogen is supplied to a reactor 6 through a line 5. This reactor is filled with one or more fixed catalyst beds. Under the conditions prevailing in said reactor the oil blend introduced is desulphurized and subsequently supplied to a reactor 8 through a line 7. The remainder of the residual fraction is supplied to the line 7 through a line 9. In the reactor 8 and the reactors 10 and 11 (each reactor contains one or more catalyst beds) connected thereafter, the oil is desulphurized further and the product is discharged through a line 12.
[0019] The resultant product can be separated into gas and liquid in the known manner and, if desired, the resultant desulphurized liquid can be separated by distillation into desulphurized residual fraction and desulphurized distillate fraction.
Example I
[0020] To 100 parts of flashed distillate with a sulphur content of 2.3% by weight and a metal content of 2 parts by weight per million (ppm), 36 parts of DAO having a sulphur content of 2.7% by weight and a metal content of 40 ppm are added. The resultant blend has a metal content of 12.1 ppm and a sulphur content of 2.4% by weight. The blend is passed downwards over a catalyst in a first reactor in the presence of hydrogen, in which step the metal content of the blend is reduced to < ppm.
[0021] The catalyst consisted of an alumina carrier with a surface area of 246 m2/g and a pore volume of 0.6 ccm/g, on which 3.7% by weight of nickel oxide and 13.2% by weight of molybdenum oxide (percentages based on carrier) had been deposited. The catalyst had been sulphided before use.
[0022] To the 136 parts of demetallized stream a further 54 parts of the above-mentioned DAO are subsequently added, with the result that the metal content of the blend is again brought to 12.1 ppm. This blend is passed to a second reactor with identical desulphurization catalyst and desulphurized therein to a final sulphur content of 0.45% by weight. In order to maintain the sulphur content at said level the reactor temperatures are gradually increased during the test. At the same time the metal content falls to <1 ppm. The conditions are summarized in the following table.
[0023] By maintaining the above-mentioned method of operation a catalyst life of 12,000 hours is obtained; subsequently a rapid deactivation of the catalyst occurs.
Example II
[0024] In a comparative test the same quantity of sulphur as in Example I, i.e. ΔSfeed-product equalling 1.95% by weight of S, is removed from 190 parts of DAO (identical with that of Example I, metal content 40 ppm, sulphur content 2.7% by weight), now without dilution with flashed distillate and without downstream addition of DAO. Use is made of a desulphurization catalyst identical to that described in Example I.
[0025] As a consequence of the high metal content of the DAO the catalyst life is now drastically limited to 1750 hours, or about 15% of the life obtained in Example I. Subsequently a rapid deactivation of the catalyst occurs.
Example III
[0026] In a comparative test 100 parts of flashed distillated and 90 parts of DAO (both identical with that used in Example I) are completely intermixed and passed as such over a desulphurization catalyst (identical with that described in Example I). The sulphur content and metal content of this mixture were 2.5% by weight and 20 ppm respectively. The same quantity of sulphur is removed as in Example I) (ΔSfeed- product 1.95% by weight).
[0027] The life of the desulphurization catalyst is now 5,900 hours, 49% of that obtained in Example I. Subsequently a rapid deactivation of the catalyst occurs.
Example IV
[0028] In a comparative test 100 parts of flashed distillate and 90 parts of DAO (both identical with that used in Example I) are completely intermixed and passed as such over a Ni/Mo desulphurization catalyst (identical with that of Example I). The S-content and the metal content of this mixture were 2.5% by weight and 20 ppm respectively.
1. A process for the catalyst hydrodesulphurization of a residual fraction of a hydrocarbon
oil where the residual fraction has a high metal content, characterized in that a
blend of part of said residual fraction having a high metal content and at least part
of a distillate fraction of a hydrocarbon oil which distillate fraction has a lower
metal content, is passed over a catalyst in the presence of hydrogen, and the remainder
of the residual fraction is supplied to the catalyst at one or more downstream points.
2. A process as claimed in claim 1, characterized in that the hydrocarbon oil is a
mineral oil.
3. A process as claimed in claims 1-2, characterized in that the residual fraction
is a deasphalted vacuum residue of a mineral oil.
4. A process as claimed in any one of the preceding claims, characterized in that
the distillate fraction of a hydrocarbon oil is a vacuum distillate fraction.
5. A process as claimed in claim 4, characterized in that the vacuum distillate fraction
is a flashed distillate.
6. A process as claimed in claim 5, characterized in that all the flashed distillate
becoming available in the vacuum distillation for the preparation of the relevant
residual fraction is incorporated into the blend with part of the residual fraction.
7. A process as claimed in any one of the preceding claims, characterized in that
the catalyst contains cobalt and/or nickel together with molybdenum and/or tungsten
(and/or compounds of these metals) on a carrier.
8. A process as claimed in claim 7, characterized in that the catalyst contains 2-6%
by weight of nickel (calculated as oxide) and 8-16% by weight of molybdenum (calculated
as oxide) on an alumina carrier having a surface area of 100-300 m2/g and a pore volume of 0.3-0.7 ccm/g.
9. A process as claimed in any one of the preceding claims, characterized in that
the oil to be desulphurized and the hydrogen are passed over the catalyst in the same
direction.
10. A process as claimed in any one of the preceding claims, characterized in that
the hydrodesulphurization is carried out at a temperature of 300-450°C, a total pressure
of 45-150 bar. A hydrogen partial pressure of 30-120 bar, a space velocity of 0.1-8.0
kg of feed per kg of catalyst per hour and a quantity of hydrogen of 250-2000 nl per
litre of feed.
11. A process as claimed in claim 10, characterized in that the hydrodesulphurization
is carried out at a temperature of 330-390°C, a total pressure of 70-95 bar, a hydrogen
partial pressure of 50-80 bar, a space velocity of 0.2-0.4 kg of feed per kg of catalyst
per hour and a quantity of hydrogen of 400-900 nl per litre of feed.
1. Un procédé pour l'hydrodésulfuration catalytique d'une fraction résiduelle d'une
huile d'hydrocarbures, la fraction résiduelle ayant une haute teneur en métal, caractérisé
en ce qu'un mélange d'une partie de cette fraction résiduelle ayant une haute teneur
en métal et d'au moins une partie d'une fraction de distillation d'une huile d'hydrocarbures,
cette fraction de distillation ayant une plus basse teneur en métal, est passé sur
un catalyseur en présence d'hydrogène, et on fait arriver le reste de la fraction
résiduelle en contact avec le catalyseur à un ou plusieurs points en aval.
2. Un procédé selon la revendication 1, caractérisé en ce que l'huile d'hydrocarbures
est une huile minérale.
3. Un procédé selon l'une des revendications 1 et 2, caractérisé en ce que la fraction
résiduelle est un résidu sous vide désasphalté d'une huile minérale.
4. Un procédé selon l'une quelconque des revendications précédentes, caractérisé en
ce que la fraction de distillation d'une huile d'hydrocarbures est une fraction de
distillation sous vide.
5. Un procédé selon la revendication 4, caractérisé en ce que la fraction de distillation
sous vide est un distillat de distillation éclair.
6. Un procédé selon la revendication 5, caractérisé en ce que tout le distillat de
distillation éclair devenant disponible dans la distillation sous vide pour la préparation
de la fraction résiduelle concernée est incorporé dans le mélange avec une partie
de la fraction résiduelle.
7. Un procédé selon l'une quelconque des revendications précédentes, caractérisé en
ce que le catalyseur contient du cobalt et/ou du nickel en même temps que du molybdène
et/ou du tungstène (et/ou des composés de ces métaux) sur un support.
8. Un procédé selon la revendication 7, caractérisé en ce que le catalyseur contient
2-6% en poids de nickel (en calculant en oxyde) et 8-16% en poids de molybdène (en
calculant en oxyde) sur un support d'alumine ayant une surface spécifique de 100-300
m2/g et un volume de pores de 0,3-0,7 cm3/g.
9. Un procédé selon l'une quelconque des revendications précédentes, caractérisé en
ce que l'huile à désulfurer et l'hydrogène sont passés sur le catalyseur dans la même
direction.
10. Un procédé selon l'une quelconque des revendications précédentes, caractérisé
en ce que l'hydrodésulfuration est effectuée à une température de 300-450°C, une pression
totale de 45-150 bars, une pression partielle d'hydrogène de 30-120 bars, une vitesse
spatiale de 0,1-8,0 kg de charge par kg de catalyseur et par heure et une quantité
d'hydrogène de 250-2000 litres (TPN) par litre de charge.
11. Un precédé selon la revendication 10, caractérisé en ce que l'hydrodésulfuration
est effectuée à une température de 330-390°C, une pression totale de 70-95 bars, une
pression partielle d'hydrogène de 50-80 bars, une vitesse spatiale de 0,2-0,4 kg de
charge par kg de catalyseur et par heure et une quantité d'hydrogène de 400-900 litres
(TPN) par litre de charge.
1. Ein Verfahren für die katalytische hydrierende Entschwefelung einer Rückstandsfraktion
eines Kohlenwasserstofföls, wo die Rückstandsfraction einen hohen Metallgehalt aufweist,
dadurch gekennzeichnet, dass ein Gemisch eines Teils der genannten Rückstandsfraktion,
die einen hohen Metallgehalt aufweist, und zumindest ein Teil einer Destillatfraction
eines Kohlenwasserstofföls, welche Destillatfraktion einen niedrigeren Metallgehalt
aufweist, über einen Katalysator in Gegenwart von Wasserstoff geleitet wird und der
Rest der Rückstandsfraktion dem Katalysator an einer oder mehreren Stellen stromabwärts
zugeführt wird.
2. Ein Verfahren wie in Anspruch 1 beansprucht, dadurch gekennzeichnet, dass das Kohlenwasserstofföl
ein Mineralöl ist.
3. Ein Verfahren wie in den Ansprüchen 1 bis 2 beansprucht, dadurch gekennzeichnet,
dass die Rückstandsfraktion ein entasphaltierter Vakuumrückstand eines Mineralöls
ist.
4. Ein Verfahren wie in irgendeinem der vorangehenden Ansprüche beansprucht, dadurch
gekennzeichnet, dass die Destillatfraktion eines Kohlenwasserstofföls eine Vakuumdestillatfraktion
ist.
5. Ein Verfahren wie in Anspruch 4 beansprucht, dadurch gekennzeichnet, dass die Vakuumdestillatfraktion
ein Kurzwegdestillat (Flash- destillat) ist.
6. Ein Verfahren wie in Anspruch 5 beansprucht, dadurch gekennzeichnet, dass das gesamte
bei der Vakuumdestillation zur Herstellung der relevanten Rückstandsfraktion verfügbar
werdende Kurzwegdestillat dem Gemisch mit einem Teil der Rückstandsfraktion einverleibt
wird.
7. Ein Verfahren wie in irgendeinem der Vorangehenden Ansprüche beansprucht, dadurch
gekennzeichnet, dass der Katalysator Kobalt und/oder Nickel zusammen mit Molybdän
und/oder Wolfram (und/oder Verbindingen dieser Metalle) auf einem Träger enthält.
8. Ein Verfahren wie in Anspruch 7 beansprucht, dadurch gekennzeichnet, dass der Katalysator
2 bis 6 Gewichtsprozent Nickel (als Oxid gerechnet) und 8 bis 16 Gewichtsprozent Molybdän
(als Oxid gerechnet) auf einem Aluminiumträger mit einer Oberfläche von 100 bis 300
m2/g und mit einem Porenvolumen von 0,3 bis 0,7 ccm/g enthält.
9. Ein Verfahren wie in irgendeinem der vorangehenden Ansprüche beansprucht, dadurch
gekennzeichnet, dass das zu entschwefelnde Öl und der Wasserstoff über den Katalysator
in derselben Richtung geleitet werden.
10. Ein Verfahren wie in irgendeinem der vorangehenden Ansprüche beansprucht, dadurch
gekennzeichnet, dass die hydrierende Entschwefelung bei einer Temperatur von 300 bis
450°C, einem Gesamtdruck von 45 bis 150 bar, einem Wasserstoffpartialdruck von 30
bis 120 bar, einer Raumgeschwindigkeit von 0,1-8,0 kg Einsatzmaterial je kg Katalysator/h
und mit Wasserstoff in einer Menge von 250 bis 2000 NI/I Einsatzmaterial durchgeführt
wird.
11. Ein Verfahren wie in Anspruch 10 beansprucht, dadurch gekennzeichnet, dass die
hydrierende Entschwefelung bei einer Temperatur von 330 bis 390°C, einem Gesamtdruck
von 70 bis 95 bar, einem Wasserstoffpartialdruck von 50 bis 80 bar, einer Raumgeschwindigkeit
von 0,2 bis 0,4 kg Einsatzmaterial je kg Katalysator/h und mit Wasserstoff in einer
Menge von 400 bis 900 NI/I Einsatzmaterial durchgeführt wird.