EP0026508B1 - Process and apparatus for the demetallization of a hydrocarbon oil - Google Patents

Process and apparatus for the demetallization of a hydrocarbon oil Download PDF

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Publication number
EP0026508B1
EP0026508B1 EP19800200807 EP80200807A EP0026508B1 EP 0026508 B1 EP0026508 B1 EP 0026508B1 EP 19800200807 EP19800200807 EP 19800200807 EP 80200807 A EP80200807 A EP 80200807A EP 0026508 B1 EP0026508 B1 EP 0026508B1
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EP
European Patent Office
Prior art keywords
catalyst
hydrocarbon oil
demetallization
hydrogen
bed
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP19800200807
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German (de)
English (en)
French (fr)
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EP0026508A1 (en
Inventor
Wouter Cornelis Van Zijll Langhout
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Publication of EP0026508A1 publication Critical patent/EP0026508A1/en
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Publication of EP0026508B1 publication Critical patent/EP0026508B1/en
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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
    • 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 a process for the demetallization of a hydrocarbon oil by passing said oil together with hydrogen over one or more fixed beds of a demetallization catalyst.
  • 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 (short residue) is deasphalted, in which process deasphalted vacuum residue of a mineral oil (also referred to as DAO below) and asphalt are obtained.
  • the heavier fractions obtained in the vacuum distillation (also referred to as vacuum distillate fractions) and the residual fractions, in particular DAO, can be used as heavy fuel or as feedstock for catalytic cracking.
  • the sulphur is very suitably removed with catalysts suitable therefor in the presence of hydrogen. Said catalysts are deactivated rapidly if the fraction to be desulphurized contains a considerable quantity of metal.
  • the metal content and the tendency to coke deposition of the feed to be used must be as low as possible in order to prevent rapid deactivation of the cracking catalyst.
  • a hydrocarbon oil to be desulphurized should be demetallized to a metal content below about 20 ppm, and this applies in particular to residual fractions, since the latter usually have metal contents which are considerably higher than 20 ppm.
  • hydrodesulphurization For the demetallization of hydrocarbon oils in the presence of hydrogen (hydro-demetallization) specific catalysts exist which possess a high activity for demetallization but only a low capacity for desulphurization. Consequently, the hydrocarbon oil obtained in the demetallization will in many cases still have to be desulphurized, in order to obtain the desired demetallized and desulphurized hydrocarbon oils.
  • the hydrodesulphurization is very suitably carried out by means of catalysts suitable therefore which as stated above, are not resistant to quantities of metal in the feed of about 20 ppm or more.
  • demetallization catalysts have a relatively short life, since after a relatively short time, as a result of the quantities of metals and coke which originate from the hydrocarbon oil and have been deposited on the catalyst, the catalyst is deactivated and such a high pressure drop across the demetallization catalyst occurs that said catalyst cannot be used further and must be removed and/or regenerated.
  • deactivated catalyst It is possible to use a fresh quantity of demetallization catalyst which is contained, for example, in a different parallel-connected reactor than the deactivated catalyst and to regenerate and/or remove the deactivated demetallization catalyst.
  • this method has the drawback that for the regeneration and/or removal from the reactor of the deactivated demetallization catalyst this reactor must be opened or at least the hydrogen present therein must be replaced by air.
  • this reactor On a site where a number of reactors are located in which hydrotreatments at high pressure and temperature are carried out, it is, for safety reasons, undesirable to shut down one of the reactors separately and replace the hydrogen therein by an oxygen-containing gas. The aim will be to close down the whole plant simultaneously for the regeneration and/or removal of the demetallization catalyst.
  • the invention provides a process for the hydrodemetallization of a hydrocarbon oil, in which process the time during which a demetallization catalyst can be used without it being necessary to be removed and/or regenerated, is prolonged considerably.
  • the invention relates to process for the demetallization of a hydrocarbon oil by passing said oil together with hydrogen over one or more fixed beds of a demetallization catalyst, which process is characterized in that whenever that catalyst portion which is first contacted with the hydrocarbon oil is deactivated the point of supply of the hydrocarbon oil is moved downstream, at least part of the original supply of hydrogen being maintained over the entire catalyst.
  • Any hydrocarbon oil to be demetallized can serve as feed for the process according to the invention.
  • crude oil oil from which the volatile products are removed (topped crude oil), oil from which light products are removed by distillation at atmospheric pressure (so-called long residue), shale oils, oils obtained from tar sands. Preference is given to residual fractions, as defined above.
  • Demetallization catalysts are known; they usually consist of oxidic carriers on which one or more metals with hydrogenation activity (or compounds of said metals) are optionally deposited.
  • oxidic carriers on which one or more metals with hydrogenation activity (or compounds of said metals) are optionally deposited.
  • use is very suitably made of catalysts of the type described in the Dutch patent application 7309387.
  • Said catalysts contain one or more metals with hydrogenation activity on a carrier and fulfil the following requirements:
  • the catalyst contains very suitably, metals with hydrogenation activity selected from the group consisting of nickel, cobalt, molybdenum, vanadium and tungsten, and particularly preference is given to catalysts which contain at least one metal of the group consisting of nickel and cobalt and at least one metal of the group consisting of molybdenum, vanadium and tungsten. Catalysts containing nickel and vanadium are particularly suitable.
  • the metals are preferably present as their oxides or sulphides.
  • Alumina and silica-alumina are very suitable as carriers. Preference is given to carriers completely or substantially completely consisting of silica.
  • Very suitable catalysts for the hydrodemetallization according to the invention are those described in the Dutch patent application 7316396. Said catalysts contain 0.1-15 parts by weight of the metal combination nickel- vanadium per 100 parts by weight of a silica carrier and have a loss on ignition, determined under standard conditions, of less than 0.5% by weight.
  • Catalysts as described in the Dutch patent application 7412155 are also very suitable.
  • the latter catalysts fulfil the above-mentioned requirements and are obtained by the noduliz- ing technique; they have a pore volume, present in pores having a diameter above 50 nm, of at least 0.2 ml/g.
  • hydrocarbon oil to be demetallized has a high metal content
  • catalyst silica on which no metals with hydrogenation activity have been deposited, as described in the Dutch patent application 7607552.
  • the process according to the invention is carried out under conditions which are usual for hydrodemetallization.
  • the hydrocarbon oil to be demetallized (which in most cases is for at least 80 vol.% in the liquid phase) together with hydrogen is very suitably passed in downward direction over the catalyst at a temperature between 300 and 450°C (preferably between 350 and 425°C), a total pressure between 75 and 250 bar (preferably between 100 and 200 bar), a hydrogen partial pressure between 35 and 120 bar (preferably between 50 and 100 bar), a space velocity of 0.1-25 parts by volume of fresh feed per part by volume of catalyst per hour and a hydrogen/feed ratio of 100-2000 (preferably 200-1500) N 1 of H z/ kg of feed.
  • the hydrogen required for the hydrodemetallization may be a hydrogen containing gas stream, such as a reformer off-gas stream, or a mainly pure hydrogen.
  • the hydrogen-containing gases preferably contain at least 60% by volume of hydrogen.
  • the demetallization catalyst may be present in one fixed bed, but is preferably present in several serially connected fixed beds.
  • the fixed beds can be located in one or more reactors.
  • the size of the catalyst beds is very suitably so chosen that the supply point of hydrocarbon oil to be demetallized is moved to a place between an exhausted catalyst bed and the next fresh catalyst bed.
  • the catalyst After the furthest downstream portion of the catalyst is also deactivated, the catalyst must be taken out of service and can be regenerated and/or removed. During regeneration the coke deposits and the metal deposits (which in many cases mainly consist of vanadium and to a lesser extent of nickel) must be at least partly removed.
  • the regeneration is very suitably carried out by the methods described in the Dutch patent applications 7511993, 7703181 and 7703180.
  • the deactivated catalyst is extracted with an aqueous solution of a mineral acid (for example sulphuric acid), which extraction is very suitably preceded by a treatment with a reducing agent or is carried out in the presence of a reducing agent. Sulphur dioxide is very suitable as reducing agent.
  • a mineral acid for example sulphuric acid
  • the carrier of the catalyst is resistant to an aqueous solution of mineral acid (i.e. consists of, for example, silica)
  • the catalyst can be reused after removal of the coke, sulphur and metals, optionally after application of the above-mentioned metals with hydrogenation activity.
  • the carrier is not resistant to an aqueous solution of a mineral acid (i.e. consists, for example, of alumina) regeneration in the above-mentioned manner is impossible. In that case it is also possible, however, to carry out the treatment with mineral acid in order to recover the metals deposited from the hydrocarbon oil. Said metals can of course also be recovered from the extract obtained in the treatment with an aqueous mineral acid solution of deactivated catalysts, the carriers of which are resistant to a treatment of this type.
  • a mineral acid i.e. consists, for example, of alumina
  • the demetallized hydrocarbon oil obtained in the process according to the invention can be used for any desired purpose.
  • the demetallization need of course not be complete and a quantity of metal may still be present in the demetallized product.
  • catalysts For the hydrodesulphurization of heavy hydrocarbon fractions, such as residual fractions, specific catalysts are known which can be used for a long time without replacement or regeneration of the catalyst being necessary as a result of deposition of coke and high-molecular components (such as resins, poly- aromatics and asphaltenes) from the feed. Catalysts as described in the Dutch patent application 7010427 are very suitable.
  • the particles of said catalysts have a pore volume above 0.30 ml/g, of which pore volume less than 10% is present in pores having a diameter above 100 nm, and the catalyst particles have a specific pore diameter expressed in nm from 7.5xd O-9 to 17xd O-9 , in which d represents the specific particle diameter in mm.
  • Said catalysts very suitably contain a carrier on which one or more metals chosen from the group consisting of nickel, cobalt, tungsten and molybdenum, and in particular one metal of the group consisting of nickel and cobalt and one metal of the group consisting of tungsten and molybdenum, are deposited.
  • Catalysts containing nickel or cobalt together with molybdenum are particularly suitable.
  • the metals are preferably present as their oxides or sulphides.
  • Very suitable carriers are silica, silica-alumina and in particular alumina.
  • the hydrodesulphurization is carried out under the usual conditions.
  • the demetallized hydrocarbon oil to be desulphurized together with the hydrogen-containing gas obtained in the demetallization (to which extra hydrogen is added, if desired) is very suitably passed in downward direction over the catalyst at a temperature between 350 and 475°C (preferably between 385 and 445°C), a total pressure between 75 and 250 bar (preferably between 100 and 225 bar), a hydrogen partial pressure between 35 and 120 bar (preferably between 50 and 100 bar), a space velocity of 0.1-25 (preferably 0.2-5) parts by volume of feed per part by volume of catalyst and a hydrogen/feed ratio of 150-2000 (preferably 250-1500) N1 of H Z /kg of feed.
  • the desulphurization catalyst is very suitably contained in one or more fixed beds which, if desired, are located in several serially connected reactors.
  • the demetallization catalyst or the desulphurization catalyst When the demetallization catalyst or the desulphurization catalyst is deactivated, the whole plant is closed down and the demetallization catalyst and desulphurization catalyst are both removed and/or regenerated. For economic reasons the aim will be to choose the quantities of demetallization catalyst and desulphurization catalyst in such a manner that both are deactivated about simultaneously, since in that manner no or only a small portion of active catalyst is removed and/or subjected to a regeneration process.
  • the product obtained after the desulphurization is separated from the hydrogen-containing gas in the usual manner; if desired, said gas can be recycled to the process afer complete or partial removal of H 2 S and any other impurities.
  • the invention also relates to an apparatus consisting of one or more serially connected reactors each of which can be filled with one or more fixed catalyst beds, the first bed of the first reactor having an inlet for a gas and an inlet for a hydrocarbon oil, characterized in that at least two inlets for hydrocarbon oil is/are present downstream, and that each hydrocarbon oil inlet can be separately connected or closed.
  • Each of the reactors R1, R2 and R3 contains two fixed beds of demetallization catalyst (1, 2, 3, 4, 5 and 6). Hydrogen is supplied to the bed 1 in reactor R1 through a line 7, passes the beds 2, 3, 4, 5 and 6 consecutively and leaves reactor R3 through a line 8 together with demetallized hydrocarbon oil. Fresh hydrocarbon oil is supplied through a line 9 and is initially supplied to bed 1 via an open valve 10 and passes through the beds 1, 2, 3, 4, 5 and 6 consecutively. Valves 11, 12, 13, 14 and 15 are closed. After the demetallization catalyst in bed 1 is deactivated, valve 11 is opened and valve 10 is closed.
  • the hydrocarbon oil to be demetallized is then supplied to bed 2 and passes through the beds 2, 3, 4, 5 and 6 consecutively.
  • bed 2 When bed 2 is deactivated, valve 12 is opened and valve 11 is closed and the hydrocarbon oil to be demetallized is supplied to bed 3.
  • the hydrocarbon oil to be demetallized is supplied to the beds 4, 5, 6 whenever the preceding bed is deactivated.
  • bed 6 After bed 6 is also deactivated, the hydrocarbon oil and hydrogen streams are interrupted and the catalyst in reactors R 1' R 2 and R 3 is replaced or regenerated.
  • the resultant demetallized hydrocarbon oil and the hydrogen-containing gas which become available through a line 8 from reactor R3 are passed without further purification through the reactors R4 and R5, each containing two beds of a desulphurization catalyst.
  • the desulphurized and demetallized hydrocarbon oil and the hydrogen-containing gas becoming available from reactor R5 through a line 16 can be separated and purified by conventional methods.
  • pressure, temperature and space velocity conditions suitable for demetallization are maintained in reactors R 1 , R 2 and R 3 and conditions suitable for desulphurization are maintained in reactors R4 and R5.
  • beds 1-6 in the reactors R1, R2 and R3 are filled with a demetallization catalyst.
  • Said catalyst contains 0.6% by weight of nickel (as oxide) and 1.9% by weight of vanadium (as oxide) on silica as carrier, has a specific average pore diameter of 13.6 nm, a specific average particle diameter of 2.2 mm, a specific surface area of 262 m 2 /g and a pore volume of 0.78 ml/g, of which pore volume 0.3% consists of pores having a diameter above 100 nm.
  • the catalyst Before use the catalyst is sulphided by passing over it a gasoil containing 1.6% by weight of sulphur, at a space velocity of 1 kg/litre of catalyst/h, a temperature of 350°C and a hydrogen pressure of 50 bar.
  • the reactors R4 and R5 are filled with a desulphurization catalyst.
  • This catalyst contains 3.6% by weight of nickel (as oxide) and 8.9% by weight of molybdenum (as oxide) on alumina as carrier, and has a specific average pore diameter of 20.2 nm, a specific average particle diameter of 1.5 mm, a specific surface area of 183 m 2 /g and a pore volume of 0.54 ml/g, of which less than 0.4% is present in pores having a diameter above 100 nm.
  • this desulphurization catalyst is sulphided in the same way as the demetallization catalyst.
  • a deasphalted vacuum residue of a mineral oil (DAO) containing 40 ppm of vanadium and 2.7% by weight of sulphur is subsequently passed through the reactors R1-R5 at a space velocity of 0.29 kg/I of catalyst/h both for the demetallization catalyst and the desulphurization catalyst, at a temperature of 390°C, a hydrogen partial pressure of 70 bar and a gas space velocity of 1000 NI/kg of feed.
  • the feed inlet is moved to the next bed of demetallization catalyst, the hydrogen stream being maintained over all the beds.
  • the test is interrupted after unacceptable pressure drop occurs while the feed is being supplied to bed 6; this is 12,000 hours after the start of the test.
  • the product obtained contains 1 ppm of vanadium and 0.5% by weight of sulphur.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP19800200807 1979-09-26 1980-08-28 Process and apparatus for the demetallization of a hydrocarbon oil Expired EP0026508B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL7907142A NL191763C (nl) 1979-09-26 1979-09-26 Werkwijze voor ontmetalliseren van een koolwaterstofolie.
NL7907142 1979-09-26

Publications (2)

Publication Number Publication Date
EP0026508A1 EP0026508A1 (en) 1981-04-08
EP0026508B1 true EP0026508B1 (en) 1983-07-20

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ID=19833914

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EP19800200807 Expired EP0026508B1 (en) 1979-09-26 1980-08-28 Process and apparatus for the demetallization of a hydrocarbon oil

Country Status (9)

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EP (1) EP0026508B1 (nl)
JP (1) JPS5655489A (nl)
AU (1) AU538217B2 (nl)
CA (1) CA1157412A (nl)
DE (1) DE3064280D1 (nl)
MX (1) MX155344A (nl)
NL (1) NL191763C (nl)
NZ (1) NZ195045A (nl)
SG (1) SG32384G (nl)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105992809A (zh) * 2013-12-23 2016-10-05 道达尔销售服务公司 用于从石油馏分中除去芳族化合物的改善的方法

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2570385B1 (fr) * 1984-09-14 1987-08-21 Raffinage Cie Francaise Procede d'hydrotraitement de charges d'hydrocarbures et catalyseur pour la mise en oeuvre de ce procede
FR2650759B1 (fr) * 1989-08-08 1991-10-31 Inst Francais Du Petrole Masse de captation a base de nickel pour l'elimination de l'arsenic et du phosphore contenus dans les coupes d'hydrocarbures liquides, sa preparation et son utilisation
FR2686617B1 (fr) * 1992-01-28 1994-03-18 Institut Francais Petrole Procede d'hydrogenation selective de charge hydrocarbonee avec des lets catalytiques mis en óoeuvre successivement.
AU688610B2 (en) * 1994-11-16 1998-03-12 Shell Internationale Research Maatschappij B.V. Process for improving lubricating base oil quality
EP0712922B1 (en) 1994-11-16 2000-02-23 Shell Internationale Researchmaatschappij B.V. Process for improving lubricating base oil quality
US20060070918A1 (en) * 2004-10-01 2006-04-06 Mayis Seapan Method to extend the utilization of a catalyst in a multistage reactor system
DE102007059243A1 (de) * 2007-12-07 2009-06-10 Uhde Gmbh Verfahren zur Entschwefelung olefinhaltiger Einsatzstoffe
DE102009032802A1 (de) * 2009-07-10 2011-01-13 Uhde Gmbh Verfahren zur Entschwefelung olefinhaltiger Einsatzstoffe durch Regelung des Olefinanteils
FR2970260B1 (fr) * 2011-01-10 2014-07-25 IFP Energies Nouvelles Procede d'hydrotraitement de charges lourdes d'hydrocarbures avec des reacteurs permutables incluant au moins une etape de court-circuitage d'un lit catalytique
CA2990021A1 (en) * 2015-07-17 2017-01-26 Exxonmobil Research And Engineering Company Production of low sulfur gasoline

Family Cites Families (6)

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Publication number Priority date Publication date Assignee Title
US3206395A (en) * 1963-01-21 1965-09-14 Pullman Inc Desulfurization product recovery process
US3563887A (en) * 1968-10-25 1971-02-16 Gulf Research Development Co Asphaltene hydrodesulfurization with small catalyst particles disposed in a guard chamber-main reactor system
GB1388714A (en) * 1971-04-01 1975-03-26 Exxon Research Engineering Co Process for the conversion of metal-contaminated hydrocarbon feedstocks
NL175732C (nl) * 1972-07-07 Shell Int Research Werkwijze voor het katalytisch demetalliseren van residuale koolwaterstofolien en het verder katalytisch omzetten van de hierbij verkregen olie.
DE2329700C3 (de) * 1973-06-09 1982-04-15 Basf Ag, 6700 Ludwigshafen Verfahren zur hydrierenden Raffination und/oder hydrierenden Spaltung kohlenwasserstoffhaltigem Einsatzmaterial
US4017382A (en) * 1975-11-17 1977-04-12 Gulf Research & Development Company Hydrodesulfurization process with upstaged reactor zones

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105992809A (zh) * 2013-12-23 2016-10-05 道达尔销售服务公司 用于从石油馏分中除去芳族化合物的改善的方法

Also Published As

Publication number Publication date
EP0026508A1 (en) 1981-04-08
AU6266480A (en) 1981-04-09
JPS5655489A (en) 1981-05-16
AU538217B2 (en) 1984-08-02
JPH0138157B2 (nl) 1989-08-11
NL191763B (nl) 1996-03-01
NL191763C (nl) 1996-07-02
CA1157412A (en) 1983-11-22
MX155344A (es) 1988-02-19
NL7907142A (nl) 1981-03-30
DE3064280D1 (en) 1983-08-25
NZ195045A (en) 1983-02-15
SG32384G (en) 1985-06-07

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