EP0181253B1 - Verfahren zur katalytischen Wasserstoffbehandlung von schweren Kohlenwasserstoffen in festem oder bewegendem Bett mit Injektion einer Metallverbindung in die Ladung - Google Patents

Verfahren zur katalytischen Wasserstoffbehandlung von schweren Kohlenwasserstoffen in festem oder bewegendem Bett mit Injektion einer Metallverbindung in die Ladung Download PDF

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EP0181253B1
EP0181253B1 EP85402042A EP85402042A EP0181253B1 EP 0181253 B1 EP0181253 B1 EP 0181253B1 EP 85402042 A EP85402042 A EP 85402042A EP 85402042 A EP85402042 A EP 85402042A EP 0181253 B1 EP0181253 B1 EP 0181253B1
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charge
process according
metal
molybdenum
compound
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French (fr)
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EP0181253A1 (de
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Jean-Claude Plumail
Jean-François Le Page
Pierre Giuliani
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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Classifications

    • 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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
    • 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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00

Definitions

  • the present invention relates to a process for hydrotreating heavy hydrocarbon feedstocks containing heteroatomic impurities such as for example sulfur, nitrogenous and metallic impurities, for example those containing nickel, vanadium and / or iron.
  • heteroatomic impurities such as for example sulfur, nitrogenous and metallic impurities, for example those containing nickel, vanadium and / or iron.
  • atmospheric distillation residues vacuum distillation residues
  • heavy crude oils deasphalted oils
  • braised and asphalts diluted with an aromatic distillate. coming for example from a catalytic cracking process (light cycle oil) and carbon hydrogenates.
  • This process consists in treating with hydrogen a charge of heavy hydrocarbons in contact with at least one fixed or mobile bed of a heterogeneous catalyst containing an alumina support and at least one catalytic metal or compound of catalytic metal of l '' at least one of the metals of groups VB, VI B and VIII of the periodic table of the elements (Handbook of Chemistry and Physics 37 th edition, 1956 pages 392-393, CRC Press), said alumina support having a pore volume of 0.85 to 2 cm 3 x g- 1 and a specific surface of 80 to 250 m 2 x g- 1 , the said process being characterized in that the hydrocarbon charge to be treated is added with hydrogen added sufficient quantity to carry out the hydrotreatment reaction, continuously or periodically, at least one compound of at least one metal chosen from the group formed by halides, oxyhalides, oxides, polyacids and polyacid salts of the metals of the metals group formed by the metals of groups VI B, VII B and VIII of the periodic classification of the elements
  • the purpose of refining hydrocarbon cuts is to convert heavy molecules into lighter molecules and to eliminate the maximum of sulfur, nitrogen and metallic heteroatomic impurities.
  • the sulfur and nitrogen heteroatoms are generally eliminated respectively in the form of hydrogen sulphide and ammonia, these compounds do not deactivate the catalyst and are found in the effluents.
  • the metals of the charge and in particular nickel and vanadium are deposited on the surface of the catalyst, generally in the form of sulphides, thus causing a significant deactivation, and hardly reversible of the catalyst, which becomes progressively incapable of carrying out the reactions hydrodesulfurization and hydrodenitrogenation.
  • the processes for hydrotreating petroleum fractions, and in particular those distilling below 550 ° C., are well known to those skilled in the art.
  • the operations are generally carried out under hydrogen pressure, in the presence of catalysts such as oxides and sulfides of molybdenum, tungsten, nickel and cobalt, for example on alumina, at temperatures generally between 250 ° C and 450 ° C.
  • the object of the present invention is to overcome the above drawbacks and in particular to allow the use of catalysts supported on alumina, said alumina having a pore volume of 0.85 to 2 cm 3 x g- 1 and a surface specific from 80 to 250 m 2 x g- 1 in industrial hydrorefining units for longer treatment times than those obtained with the processes of the prior art, and making it possible in certain cases to avoid having to set up performs a second hydrotreatment step.
  • the compounds of the above metals chosen from the group formed by halides, oxyhalides, oxides, polyacids such as isopolyacids and heteropolyacids and the salts of these acids make it possible to obtain a clear improvement of the performance of the catalysts used and in particular of their lifetime.
  • halogenated compounds compounds containing chlorine, bromine or iodine are advantageously used in their formulas and more particularly compounds containing chlorine or iodine in their formulas.
  • molybdenum compounds will be used alone or in combination with nickel and / or cobalt compounds and, preferably, blues of molybdenum and / or phosphomolybdic acid or one of its salts will be used.
  • the metal compound which is injected into the charge of hydrocarbons to be treated is introduced for example in the form of a solution, or of suspension in an organic solvent having a solubility of at least 1% by weight in hydrocarbons under the conditions hydrotreatment, in the form of a solution or emulsion in a water-organic solvent mixture, or in the form of an aqueous solution of said compound if it has sufficient solubility in water.
  • metal compounds are used in solution in hydrocarbons or in solution in mixtures of alcohols, in particular CrC9 alcohols or in solution in water-CrC9 alcohol mixtures.
  • phosphomolybdic acid or its salts in aqueous solution, and / or molybdenum blues preferably chosen from those described in FR-A-1 099 953, in solution in a mixture of alcohols C 7 -C 9 or in a water-alcohol mixture C 7 -C 9 or in hydrocarbons, for example in a fraction of the feedstock from a previous treatment.
  • the catalysts which are used in the context of the present invention containing an alumina support with a pore volume of 0.85 to 2 cm3 ⁇ g- 1 and a specific surface of 80 to 250 m 2 x g- 1 .
  • the aluminas which can be used as a support are preferably chosen from aluminas of low or zero acidity, such as that having a heat of neutralization by absorption of ammonia preferably less than 10 calories and more particularly less than 7 calories per gram of alumina at 320 ° C under 0.04 megapascals (MPa).
  • the so-called neutral aluminas can also be characterized by their inertness with respect to cracking and coking reactions in the presence of hydrogen. Neutrality can be determined for example by the n-heptane cracking test which consists in measuring the quantity of n-heptane converted into lighter molecules under the following operating conditions:
  • the conversion is measured by analysis by gas chromatography of the liquid products.
  • a support is said to be neutral if its cracking activity (mole / hour and / m 2 of support) is less than 5 x 10 -6 at the temperature of 470 ° C and if it is less than 15 x 10- Q at a temperature of 500 ° C.
  • aluminas treated with alkali and / or alkaline-earth metals for example those having an Na 2 0 content of 1000 ppm by weight or higher can be used, as well as those thermally stabilized with rare earth metals and / or alkaline earth metals and / or silica, generally meet the neutrality criteria defined below.
  • autoclaved alumina denotes aluminas which have undergone a treatment with water or with steam called “autoclaving” at a temperature between approximately 80 ° C. and approximately 300 ° C. for approximately 5 minutes to 48 hours, preferably 1 to 6 hours.
  • the aqueous autoclaving medium contains at least one acid capable of dissolving part of the alumina of the agglomerates, or the mixture of such an acid with at least one compound providing an anion capable of combining with aluminum ions, for example a mixture of nitric acid and acetic or formic acid.
  • the autoclaving technique is for example described in French patent application FR-A-2 496 631.
  • an autoclaved alumina obtained according to the method described in European patent application EP-A-98 764 will be used.
  • the alumina support obtained is formed from a plurality of needle-like platelets, the platelets of each agglomerate being oriented generally radially with respect to each other and relative to the center of the agglomeration.
  • the aforementioned structure includes macropores and mesopores (we call mesopores, the pores of size between that of the micropores and that of the macropores: the mesopores are therefore, roughly between 10 and 100 nanometers) and practically no micropores.
  • the preferred supports are those which contain a preponderant proportion of wedge-shaped mesopores.
  • the catalytic metal or metals or compounds of catalytic metals is deposited by any known method of at least one of the metals of groups VB, VI B, and VIII of the periodic table of the elements and preferably at least one of the metals from the group formed by molybdenum, tungsten, iron, cobalt, nickel, chromium and vanadium. Preferred combinations are molybdenum + cobalt, molybdenum + nickel, tungsten + nickel, vanadium + nickel.
  • the metal content of the final catalyst used in the present invention is generally from 0.5 to 40% by weight of metals (expressed as oxide) relative to the weight of the finished catalyst. In a preferred embodiment of the invention, one of the combinations of metals mentioned above is used, the metal content then preferably being from 1 to 30% by weight of metals (expressed as oxide) relative to the weight. of the finished catalyst.
  • the catalysts described in European patent application EP-A-98 764 including the support formed from autoclaved alumina with the structure mentioned above, which have a structure identical to that of the support, and have improved resistance to clogging of mouths of pores compared for example to bimodal (macroporous and microporous) or monomodal (microporous) catalysts are preferred within the framework of the invention.
  • the support of these catalysts is inert to the n-heptane cracking test. Yielded specific activities of 0,610- 6 mol / (h. M 2) at 470 ° C and 8 x 10- 6 mole / (h. M 2) at 500 ° C.
  • the continuous or periodic injection of metal compounds, and in particular of molybdenum compounds is carried out after adding hydrogen in an amount sufficient to carry out the hydrorefining reaction of the feed.
  • the metal compound is introduced before the said charge, previously added with hydrogen, passes through the heterogeneous catalyst bed.
  • the metal compound is introduced into the charge previously added with hydrogen and previously brought to a temperature of at least 330 ° C, advantageously from 330 ° C to about 450 ° C and preferably, previously brought to a temperature of about 350 ° C to about 450 ° C.
  • the amount of the metal compound added to the charge is such that the concentration of metal added relative to the total weight of the charge is from 10 to 1500 ppm and preferably from 30 to 600 ppm.
  • this metallic compound in particular of the molybdenum compounds makes it possible, in addition to the increase in the cycle time, to keep the demetallizing activity of the catalyst constant, to improve the hydrodenitrogenation activities, d hydrodesulfurization and conversion of heavy molecules.
  • the metal compounds in particular the molybdenum compounds, decompose on the catalyst and the metal atoms (molybdenum) then attach to the surface of the catalyst, thus making it possible to avoid deactivation thereof, by continuous or periodic regeneration of the active phase.
  • the injection of the metal compounds, preferably molybdenum compounds, is in an advantageous form of the present invention carried out periodically.
  • a quantity of compound is thus introduced during a determined period into the charge, at variable intervals, for a more or less long time; for example, this compound is introduced for 1 to 30 hours every 100, 200 or 300 hours and advantageously for 10 to 20 hours every 200 hours.
  • the usual conditions for the hydrotreatment reaction are a temperature of approximately 250 to approximately 500 ° C and preferably approximately 350 to approximately 450 ° C, a pressure of approximately 5 to approximately 30 megapascals (MPa) and preferably approximately 8 to approximately 20 MPa and a flow rate of hydrocarbon feedstock per volume of catalyst and per hour (VVH) of approximately 0.1 to approximately 10 and preferably approximately 0.2 to approximately 2.
  • the flow rate of hydrogen is for example from about 50 to about 5000 liters per liter of filler and preferably from about 200 to about 3000 x 1- 1 .
  • the support for these catalysts is alumina, it is prepared according to the method described in Example 1 of patent application EP-A-98 764 and has all the characteristics described in this example. Then deposited on this support molybdenum and nickel using the method described in Example 1 of application EP-A-98 764.
  • the metal contents expressed by weight of oxide relative to the weight of the finished catalyst of the catalysts A and B obtained are the following:
  • Test 1 1 1 of catalyst A is placed in a hydrotreating pilot unit operating in a fixed bed.
  • the operating conditions for using this catalyst are as follows:
  • the petroleum cut used to carry out the test is atmospheric petroleum residue from Safaniya (Saudi Arabia), the characteristics of which are as follows:
  • the pilot unit consists of a preheating oven, allowing the charge to be brought to the desired temperature for the catalytic hydrotreatment reaction, in series with a catalytic hydrotreatment reactor comprising a fixed catalyst bed.
  • the above charge and the hydrogen are introduced into the preheating furnace so as to raise the temperature of this mixture to 400 ° C., this charge plus hydrogen mixture then passes into the catalytic hydrotreatment reactor.
  • Test 2 Under the same operating conditions, with the same apparatus and the same catalyst as that used in test 1, another test is carried out by continuously adding, in the charge-hydrogen mixture leaving the preheating oven, molybdenum, in the form of an emulsion at 5.8% by weight of molybdenum blue in a water-organic solvent mixture containing 2% by weight of water, the organic solvent consisting of a mixture of CrCg alcohols.
  • the quantity of this aquo-organic emulsion introduced into the charge is such that the molybdenum content, counted by weight of metal relative to the weight of the charge, is 100 ppm.
  • Test 1 1 I of catalyst B is placed in a pilot hydrotreatment unit operating in a fixed bed.
  • the apparatus, the operating conditions and the test load used are identical to those of test 1 of Example 1.
  • Test 2 1 I of the same catalyst B is placed in the same pilot unit, under the same operating conditions. However, in the feed, phosphomolybdic acid in aqueous solution is added at the outlet of the preheating oven before its injection into the catalytic hydrotreatment reactor. The amount of acid added is such that the molybdenum content in the feed is 50 ppm.
  • the test load is an asphalt diluted with 35% by weight of light cycle oil (LCO).
  • LCO light cycle oil
  • the charge-hydrogen mixture is brought to 410 ° C. in the preheating oven and then introduced into the catalytic hydrotreatment reactor.
  • Test 2 1 I of catalyst A is loaded into the same pilot unit and is put under the same operating conditions as those of test 1. In the same test load as that used in test 1, the output is added the molybdenum blue preheating oven in solution at 5.8% by weight in a mixture of C 7 -C 9 alcohols. The amount of solution added is such that the molybdenum content in the feed is 150 ppm by weight.
  • Test 3 This test is identical to test 2 except that the blue of molybdenum is replaced by molybdenum trioxide in a water-alcohol mixture C 7 -C 9 at 10% by weight of water and a sufficient amount of this composition is introduced to have 150 ppm by weight of molybdenum in the feed.
  • Test 4 This test is identical to test 2 with the exception that the molybdenum blue prepared using the method described in FR-A-1 099 953 is used. A sufficient amount of this compound is introduced to have 150 ppm by weight of molybdenum in the feed.
  • the hydrocarbon charge used to carry out the test is Boscan crude deasphalted with pentane (Venezuelan crude from the Orinoco belt), the characteristics of which are:
  • the charged hydrogen mixture is brought to 380 ° C. in the preheating oven and then introduced into the catalytic hydrotreatment reactor.
  • Test 2 1 1 of catalyst A is placed under the same conditions as those of test 1.
  • the test charge used is also that of test 1. But during the test, every 200 hours, for 12 hours phosphomolybdic acid in aqueous solution is added to the charge at the outlet of the preheating oven, in an amount such that the molybdenum concentration in the charge which is introduced during these 12 hours is 600 ppm by weight.
  • Test 1 1 liter of catalyst A is placed in a pilot hydrotreatment unit operating in a fixed bed.
  • the apparatus, the operating conditions and the test load used are identical to those of test 1 of Example 4.
  • Test 2 1 liter of the same catalyst A is placed in the same pilot unit, under the same operating conditions. However, in the charge-hydrogen mixture, molybdenum naphthenate is added at the outlet of the preheating oven, before its injection into the catalytic hydrotreatment reactor, in the form of a 6% by weight solution in a mixture of alcohols. C 7 -C 9 . The amount of solution added is such that the molybdenum content in the feed is 600 ppm.

Claims (11)

1. Verfahren zur Hydrobehandlung einer Charge schwerer Kohlenwasserstoffe in Kontakt mit wenigstens einem festen oder mobilen Bett von heterogenem Katalysator, umfassend einen Aluminiumoxidträger, wenigstens ein katalytisches Metall oder eine katalytische Metallverbindung von wenigstens einem der Metalle der Gruppen VB, VIB und VIII des periodischen Systems der Elemente, wobei der Aluminiumträger ein poröses Volumen von 0,85 bis 2 cm3 x g-1 und eine spezifische Oberfläche von 80 bis 250 m2 x g-1 hat, dadurch gekennzeichnet; daß man arbeitet indem man in die genannte Kohlenwasserstoff-Charge, der zuvor Wasserstoff in ausreichender Menge zugefügt wurde, um die Reaktion der Hydrobehandlung zu bewirken, und gehalten bei einer Temperatur von mindestens 330 °C, in kontinuierlicher oder periodischer Weise, wenigstens eine Verbindung wenigstens eines Metalls einführt, gewählt in der Gruppe, gebildet durch die Halogenide, die Oxihalogenide, die Oxide, die Polysäuren und die Salze von Polysäuren von Metallen der Gruppe gebildet durch die Metalle der Gruppen VIB, VIIB und VIII des periodischen Systems der Elemente, der Durchgang der genannten Charge durch das Bett des heterogenen Katalysators, wobei die gennante Verbindung in einer Menge eingeführt wird, daß der Gehalt an zugefügtem Metall in der Charge von 10 bis 1 500 ppm (in Gewicht) beträgt.
2. Verfahren gemäß Anspruch 1, in welchem der Aluminiumoxidträger gewählt ist unter Aluminiumoxiden von schwacher oder nicht vorhandener Azidität, wobei die Aluminium oxide thermisch stabilisiert sind und die Aluminiumoxide inert autoklaviert sind gegenüber dem Test der Crackung von n-Heptan.
3. Verfahren gemäß Anspruch 2, in welchem die Aluminiumoxidträger ein autoklaviertes Aluminiumoxid ist, gebildet aus einer Vielzahl von nadelförmigen Plättchen, wobei die Plättchen jedes Agglomerats im allgemeinen radial angeordnet sind untereinander gegenüber den anderen und in Bezug auf das Zentrum des Agglomerats.
4. Verfahren gemäß einem der Ansprüche 1 bis 3, in welchem die Metallverbindung in die Charge eingeführt wird in Form einer Lösung oder einer Emulsion in einer Mischung Wasser-organisches Lösungsmittel enthaltend 70 bis 99 Gew.-% organische Lösungsmittel, von Lösung in einem organischen Lösungsmittel oder von Lösung in Wasser.
5. Verfahren gemäß Anspruch 4, in welchem die Metallverbindung eingeführt wird in die Charge in Form einer Lösung oder eine Emulsion in einer Mischung Wasser-organischem Lösungsmittel, wobei das genannte organische Lösungsmittel wenigstens einen Alkohol mit 6 bis 18 Kohlenstoffatomen enthält.
6. Verfahren gemäß einem der Ansprüche 1 bis 5, in welchem die Metallverbindung eingeführt wird in die Charge in einer Menge, daß der Gehalt an zugefügtem Metall in der Charge von 30 bis 600 ppm (in Gewicht) beträgt.
7. Verfahren gemäß einem der Ansprüche 1 bis 6, in welchem die Metallverbindung, eingeführt in die Charge, eine Verbindung von Molybdän ist, gewählt in der Gruppe gebildet durch die Molybdänblau-Substanzen, Phosphomolybdänsäure und die Salze von Phosphomolybdänsäure.
8. Verfahren gemäß einem der Ansprüche 1 bis 7, in welchem der heterogene Katalysator von 1 bis 30 Gew.-% (ausgedrückt in Oxid) einer Assoziation von Nickel und Molybdän, oder von Kobalt und von Molybdän oder von Nickel und Wolfram umfasst.
9. Verfahren gemäß einem der Ansprüche 1 bis 8, in welchem die Metallverbindung in periodischer Weise in die Charge eingeführt wird.
10. Verfahren gemäß einem der Ansprüche 1 bis 8, in welchem die Metallverbindung in kontinuierlicher Weise in die Charge eingeführt wird.
11. Verfahren gemäß einem der Ansprüche 1 bis 10, in welchem die Charge von zu behandelnden Kohlenwasserstoffen gewählt ist in der Gruppe gebildet durch die Rückstände von atmosphärischer Destillation, den Rückständen von Vakuumdestillation, schweren Rohölen, entasphaltierten Ölen, den Teeren und den Asphalten, verdünnt durch ein aromatisches Destillat und den Kohlenhydrierungsprodukten und die Hydrobehandlung durchgeführt wird, bei einer Temperatur von ungefähr 250 bis ungefähr 500 °C, einem Druck von ungefähr 5 bis ungefähr 30 MPa, einer stündlichen Volumengeschwindigkeit (volume per volume per hour = VVH) von ungefähr 0,1 bis ungefähr 10 I pro Liter an Katalysator und pro Stunde und einem Wasserstoffstrom von ungefähr 50 bis ungefähr 5 000 I pro Liter an Charge. (VVH = Volumen pro Volumen pro Stunde).
EP85402042A 1984-10-24 1985-10-22 Verfahren zur katalytischen Wasserstoffbehandlung von schweren Kohlenwasserstoffen in festem oder bewegendem Bett mit Injektion einer Metallverbindung in die Ladung Expired EP0181253B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85402042T ATE36555T1 (de) 1984-10-24 1985-10-22 Verfahren zur katalytischen wasserstoffbehandlung von schweren kohlenwasserstoffen in festem oder bewegendem bett mit injektion einer metallverbindung in die ladung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8416255 1984-10-24
FR8416255A FR2572088B1 (fr) 1984-10-24 1984-10-24 Procede d'hydrotraitement catalytique d'hydrocarbures lourds, en lit fixe ou mobile, avec injection d'un compose de metal dans la charge

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EP0181253A1 EP0181253A1 (de) 1986-05-14
EP0181253B1 true EP0181253B1 (de) 1988-08-17

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US (1) US4655905A (de)
EP (1) EP0181253B1 (de)
JP (1) JPS61111394A (de)
AT (1) ATE36555T1 (de)
CA (1) CA1243975A (de)
DE (1) DE3564447D1 (de)
FR (1) FR2572088B1 (de)

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ATE36555T1 (de) 1988-09-15
JPS61111394A (ja) 1986-05-29
EP0181253A1 (de) 1986-05-14
FR2572088A1 (fr) 1986-04-25
CA1243975A (fr) 1988-11-01
FR2572088B1 (fr) 1987-07-24
DE3564447D1 (en) 1988-09-22
US4655905A (en) 1987-04-07

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