EP2479242A1 - Procédé de traitement par hydrogénation d'hydrocarbures fortement contaminées par des composants anorganiques - Google Patents

Procédé de traitement par hydrogénation d'hydrocarbures fortement contaminées par des composants anorganiques Download PDF

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Publication number
EP2479242A1
EP2479242A1 EP11151377A EP11151377A EP2479242A1 EP 2479242 A1 EP2479242 A1 EP 2479242A1 EP 11151377 A EP11151377 A EP 11151377A EP 11151377 A EP11151377 A EP 11151377A EP 2479242 A1 EP2479242 A1 EP 2479242A1
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EP
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Prior art keywords
alkali metal
compounds
catalyst
aluminosilicate
hydrogenation
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EP11151377A
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German (de)
English (en)
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EP2479242B1 (fr
Inventor
Andreas Schüppel
Heino Dr. John
Tim Dr. Bongardt
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Puralube Germany GmbH
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Puralube Germany GmbH
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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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/208—Sediments, e.g. bottom sediment and water or BSW

Definitions

  • the invention relates to a process for the hydroprocessing of highly contaminated hydrocarbons, in particular using solid particles as a protective catalyst and adsorbent with the aim of obtaining high quality lubricants, solvents and fuels.
  • the hydrocarbons used may be any carbonaceous waste streams, petroleum products, hydrocarbon oils of natural or synthetic origin, any biomass-derived liquid oils, such as pyrolysis oil containing non-distillable components.
  • the contaminated hydrocarbon fractions contain solids such as metal and heteroatom compounds, phosphorus, arsenic, nickel, vanadium, iron, lead, and the like. a., But also silica, the z. B. is present in tar sands.
  • Pyrolysis oil is formed by rapidly heating materials in an oxygen environment to form hydrocarbon-containing fluid.
  • plastics such as polyethylene, polypropylene and polystyrene made from olefin monomers are depolymerized by pyrolysis, aliphatic hydrocarbons containing solids such as additive metals and finely divided dust are produced.
  • the vaporized hydrocarbons are withdrawn and the remaining hot liquid is transferred to a stripper unit where superheated steam is used to strip additional hydrocarbons from the liquid in a second vapor stream.
  • the second vapor stream is cooled to condense the hydrocarbon portion of the vapor as a liquid in a hot separator and to separate the water vapor.
  • the liquid streams thus obtained still contain portions of interfering impurities. They are mixed with the hydrogen from the evaporator and pass through a reactor where most of the hydrogenation-damaging substances are to be collected on a hydrodemetallisation catalyst.
  • the hydrocarbon stream thus depleted of harmful contaminants then passes into a second reactor where it is hydrotreated on a hydroprocessing catalyst.
  • the effluent is condensed to obtain a suitable quality oil.
  • the remaining gaseous fraction contains hydrogen, which is recycled after separation of H 2 S and other gaseous components as recycle gas.
  • the process described above is intended to permit the desired demetallization of the contaminated hydrocarbon and includes, among others, dehalogenation, desulfurization, denitrification, olefin saturation, organic phosphorus deposition, organic silicon compounds, and the conversion of the oxygen compounds.
  • the preferred composition of the hydrodemetallization catalyst described above is an inorganic oxide material.
  • Porous or non-porous catalysts may include, but are not limited to, silica, alumina, titania, zirconia, carbon, silicon carbide, silica-alumina, diatomaceous earth, clay, magnesia, activated carbon, and molecular sieves.
  • Silica alumina is a material that may be amorphous or crystalline and consists of silica moieties, but not just a physical mixture of silica and alumina.
  • a mixture of different hydrodemetallization catalysts may be used depending on the material source for the hydrocarbon feedstream become.
  • a complex hydrocarbon feed stream mixture may require a mixture of catalysts due to the nature of the metals and solids to be deposited.
  • the catalyst comprises a metal deposited on the inorganic oxide material.
  • Suitable metals deposited on the support for hydrodemetallization activity in the form of chemical compounds of these metals include those of groups VIB and VIII of the Periodic Table of the Elements, for example chromium (Cr), molybdenum (Mo), tungsten (W), iron (Fe) , Ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), iridium (Ir), nickel (Ni), palladium (Pd), and platinum (Pt).
  • the amount of active metallic component is dependent on the particular metal and the physical and chemical properties of the particular hydrocarbon feedstock.
  • the metallic components selected from Group VIB are generally present in an amount of from one to 20 percent by weight of the catalyst, the Group VIII iron group metallic components are generally present in an amount of from 0.2 to 10 percent by weight of the catalyst, and Group VIII noble metals are generally present in an amount of from 0.1 to 5 percent by weight of the catalyst.
  • the hydrodemetallization catalyst may comprise at least one of cesium, francium, lithium, potassium, rubidium, sodium, copper, gold, silver, cadmium, mercury, and zinc.
  • the preferred composition of a hydroprocessing catalyst present in the hydroprocessing reactor may generally be characterized as comprising at least one metal having hydrogenation activity combined with a suitable refractory inorganic oxide support material of either synthetic or natural origin.
  • this catalyst can not accommodate the significantly high levels of metals and phosphorus since the pore diameters available for incorporation of the inorganic compounds and the pore volume are not large enough and some reactants from the hydrogenated hydrocarbon streams, such as phosphorus compounds, are insufficient with the chemical composition the catalyst mass can react.
  • EP 0260826A describes catalysts or precursors thereof from a ceramic body having a foam structure.
  • the catalysts are suitable for various purposes and contain, inter alia, alumina and an alkali oxide.
  • the material may still contain hydrogenation metal compounds.
  • the catalysts described are not suitable for the absorption of dirt and catalyst poisons and not intended.
  • Alumina / silicate-based catalyst carriers which have a directed, continuous pore structure in the macro and micro range. Essentially, this process consists in foaming aluminum oxide / silicate-based slip-form masses with metal pastes or powders using conventional modifiers, binders and thixotropic agents at temperatures below 100 ° C. and pH values of 7 to 12. The foamed ceramic material is then dried and fired at temperatures of 900 to 1800 ° C. However, the described material has no effect on the conversion of organic heteroatom compounds and the fixation of the resulting compounds, so that the catalyst poisons continue to get into the bed of the hydrogenation catalyst.
  • a layer of supermacroporous ceramic material based on, among other things, silica-alumina.
  • This ceramic material may also contain a coating of porous alumina and a metal from group VIB or VIII.
  • These materials are primarily suitable for collecting solid, inorganic compounds in large pores, for example inorganic Si-containing sediments, particles of zinc phosphate or zinc phosphide, but not large amounts of phosphorus from volatile organophosphorus compounds or hydrogen phosphide compounds. Furthermore, they can convert undissolved organometallic compounds and then take up. The latter go through the guard bed made of porous ceramic and further reduce the effectiveness of the hydrogenation catalysts arranged thereafter. Although the arrangement of such a protective layer extends the life of a catalyst filling, but an average duration of, for example, three months is technically not optimal.
  • EP 0412862 A1 describes a nickel-based absorbent for removing phosphorus and arsenic from liquid hydrocarbon fractions. This relates to a mass for uptake of phosphorus, which consists of 40 to 97% by mass of a porous support, which in turn contains 40 to 98.5% by mass of aluminum oxide and 1.5 to 60% of oxides of Mg, Ca, Sr, Ba, Mn, Fe, Co, Ni, Cu and Zn dissolved in the alumina, as well as, based on the total composition, 3 to 40 mass% of nickel oxide, which is brought by exchange or deposition on the support and not converted into aluminate.
  • the masses are generally thermally activated at 600 ° C or between 750 and 800 ° C.
  • the invention is based on the object in the processing of particularly highly contaminated with inorganic constituents hydrocarbons, the inorganic ingredients catalytically better than previously known and at the same time to ensure the absorption of the inorganic compounds the task. Due to the new protective material, dirt particles and catalyst poisons are to be filtered out, chemically reacted and effectively fixed, so that the hydrogenation catalyst is better protected. This results in significant advantages for the hydrogenation process and the extension of the service life of catalyst fillings.
  • catalysts and adsorbents in the form of solid particles are used for the hydroprocessing of hydrocarbons heavily contaminated with inorganic constituents in fixed bed reactors for the separation of sediments and catalyst poisons.
  • the contaminated hydrocarbon is passed over a bed of particles of a combination of adsorbent and catalyst consisting of supermacroporous alkali metal aluminosilicate and optionally loaded with hydrogenation components.
  • Suitable catalysts are, for. As described in co-pending EP patent application of Euro Support Catalyst Group B.V., Amersfoort, NL entitled “Catalytically Active Material for Hydrogenation Treatment of Hydrocarbons".
  • the bed arranged in hydrogenation reactors can be arranged according to the invention from a layer of alkali metal aluminosilicate and a subsequently arranged layer of hydrogenation metal-loaded alkali metal aluminosilicate. It is also possible to cover the entire bed with a hydrogenation metal loaded alkali metal aluminosilicate.
  • the ratio of SiO 2 to Al 2 O 3 may be 5: 95 to 80: 0, expressed in% by weight.
  • Suitable alkali constituents of the aluminosilicate are compounds of elements of main group 1 of the Periodic Table of the Elements, such as Li 2 O, Na 2 O, K 2 O, Rb 2 O and / or Cs 2 O.
  • the alkali metal aluminosilicate preferably contains 1 to 30% by mass. % Na 2 O and / or K 2 O.
  • the alkali metal aluminosilicate used according to the invention contains 0 to 10% by mass of an element of VI. Subgroup of the PSE and / or 0 to 10% by mass of the VIII. Group of the PSE.
  • the Alkalialumosilikat contains as elements of the VIII. Group of PSE 0.0 to 10 mass% iron, nickel and / or KobUbraucht and as elements of VI. Subgroup of the PSE and 0.0 to 10% by mass of molybdenum and / or tungsten.
  • the alkali metal aluminosilicate used according to the invention can be used in particles of 3 to 50 mm diameter of any shape. It has a pore volume of 0.6 to 1.5 cm 3 / g, which is present predominantly in pores with diameters of 0.01 to 3.0 mm. Its specific surface area is less than 10 m 2 / g.
  • the alkali metal aluminosilicate is prepared, for example, by forming a slurry of aluminas and silicates by mixing the powdery components with water and auxiliary stabilizers and stirring air to form fine bubble-shaped cavities, pouring the mass into molds, drying slowly to remove the water , wherein the continuous pore system is formed by large pores, and calcined at temperatures between 900 and 1800 ° C to form mullite.
  • the preparation of such known as foamed ceramic materials is known.
  • the supermacroporous aluminosilicate produced in this way is subsequently impregnated with the alkali metal compound and thermally post-treated, but it is also possible to introduce an alkali compound into the slurry, so that the desired concentration of the alkali compounds is already achieved.
  • the alkali metal aluminosilicate used according to the invention can be loaded with hydrogenation metal compounds, preferably with elements of VI. Subgroup and / or VIII. Group of the Periodic Table of the Elements, wherein the content of hydrogenation metals can be up to about 20% by mass, advantageously up to 10% by mass.
  • hydrogenation metal compounds preferably with elements of VI. Subgroup and / or VIII.
  • Group of the Periodic Table of the Elements wherein the content of hydrogenation metals can be up to about 20% by mass, advantageously up to 10% by mass.
  • sulfur-hard combinations of the hydrogenation metals molybdenum and / or tungsten and iron, cobalt or nickel are used.
  • For introducing these hydrogenation metals for. B. by impregnation of the solid carrier particles with solutions of salts of hydrogenation metals, known methods can be applied.
  • the alkali metal aluminosilicate used according to the invention when the hydrogenation metals of VI. Subgroup and / or VIII.
  • Group of the Periodic Table of the Elements contains, prior to use sulfided by known methods, for. B. by treatment with a mixture of hydrogen and hydrogen sulfide or by impregnation with sulfur organic compounds. But it can also be sulfided in situ by sulfur compounds are offered in a hydrogen atmosphere. It can also be used immediately; at high H 2 S partial pressure, the compounds of metals of the VI. and / or VIII.
  • Subgroup of the Periodic Table is converted into sulfides. Thereafter, the metals are present in the form of their sulfides, which are sulfur-resistant hydrogenation catalysts in the corresponding combinations.
  • a particular advantage of the alkali aluminate ceramic foam used is that it has large pores and a high pore volume, by which the transport reactions into the interior of the particles are not limited at all. Thus, even large molecules and agglomerated, fine inorganic dusts are flushed into the interior of the individual particles and filtered out of the hydrocarbon stream. In contrast to the usual Demetallmaschineskatalysatoren there are therefore no restrictions by the use of larger particles of dimensions of several centimeters.
  • the void volume resulting in the bed can be further used after saturation of the pores with dirt particles for the transport of the oil and the hydrogen in the reactor and is filled at the end of the operating period with other dirt particles. Thus, the early development of disturbing differential pressures over the system is avoided.
  • a spent motor oil is used as the contaminated hydrocarbon oil, and in the first zone of the bed of the combination employed in accordance with the invention preferably zinc phosphate and zinc phosphide are deposited and in the second zone preferably volatile phosphine compounds and organophosphorus compounds are reacted to alkali metal aluminosilicate and the phosphorus is chemically treated by the alkali metal aluminosilicate bound.
  • the supermacroporous alkali metal aluminosilicate without hydrogenation metal loading can also be used in the first zone, while in the second reaction zone the alkali metal aluminosilicate with hydrogenation metal loading is used.
  • the spent motor oil contains 1 to 3% by mass of zinc dialkyldithiophosphate and other additives such as calcium sulfonate. During use, the motor oil absorbs further metal compounds of lead, iron, chromium, copper.
  • the contained in the engine oil Additive Zinkdialkyldithiophosphat or whose phosphorus-containing decomposition products reaches at least z. T. with the vaporizable hydrocarbons in the reactor units (deposition and reaction zones) and is deposited immediately in the first zone as an inorganic compound. In the second reaction zone, the volatile organophosphorus decomposition products of the zinc dialkyldithiophosphate are hydrogenated.
  • Resulting compounds such as phosphoric acid and phosphine, are chemically bound to the combination of catalyst and absorbent, consisting of macroporous Alkalialumosilikat.
  • the oil contains organometallic compounds, for example, zinc, iron, chromium, copper and arsenic. These are different acting poisons for the hydrogenation catalysts. They are also on the inventive combination of catalyst and absorbent, consisting of macroporous Alkalialumosilikat decomposed. Then they are incorporated into the chemical structure of the alkali metal aluminosilicate or deposited as after their hydrogenating decomposition under the action of H 2 S and phosphorus compounds as sulfides, phosphides and phosphates inside the large channels.
  • the applied compounds transfer elements of the VI. Subgroup and the VIII. Group of the PSE their hydrogenation also on the deposited during the process inorganic metal compounds continue to the hydrodenzable hydrocarbon heteroatom compounds, so that the conversion in the easily accessible by their size pores can run even longer.
  • dirt can still deposit in the void volume of the catalyst beds until the patency through the catalyst bed leads to an excessive increase in differential pressure.
  • Phosphorus is bound primarily by the alkali metal aluminosilicate;
  • phosphorus can also be bound by the hydrogenation metals applied during production and by the metals incorporated during the process, such as zinc, iron, nickel, copper.
  • the length of the zones can be changed accordingly to extend the running times.
  • the first zone In the presence of more contaminants of sediment character, the first zone is to be extended while in the presence of first decomposable organometallic compounds that can act as catalyst poisons and must be bound before they reach the hydrogenation catalyst, the second zone must be extended.
  • Chlorine which is present in the form of organic chlorine compounds in the hydrocarbon stream, is absorbed only in minimal amount in the 2nd reaction zone. This will be this Element either decomposes only on the hydrogenation catalyst in the 3rd zone or it passes as hydrogen chloride, the second zone and the 3rd zone and is deposited after washing predominantly as HCl with the wash water. Accordingly, the alkali metal aluminosilicate is not unfavorably burdened with large amounts of chemically bound chlorine.
  • the alkali aluminate can also be charged without loading with compounds of elements of the VI. Subgroup and VIII. Group of the PSE are used. From the hydrocarbon stream of spent engine oil, large quantities of phosphorus compounds are then taken up. The metals deposited in the large pores of the alkali metal aluminosilicate, such as zinc, nickel and vanadium as sulfides and phosphides, may also become catalytically active and cause further hydrogenation of organometallic compounds. The hydrogenation effect is also not completely suppressed by the presence of ingested arsenic or lead, but the hydrogenation metals applied to the inner surface during the manufacturing process continue to transfer their hydrogen activating action to the molecules flowing through.
  • Phosphorus and arsenic are obviously not fixed to the hydrogenation metals, such as nickel, in the alkali metal aluminosilicates used, but in far greater quantities in the aluminosilicate body. About the mechanism of recording can not be said statements. Since arsenic can also be taken up by the alkali aluminosilicate foamed ceramic when combined with only low hydrogenation metal contents, an additional advantage arises by avoiding high levels of expensive heavy metal compounds in the protective catalyst used.
  • the beds are about the same size.
  • Raw material before bed 1 oil fraction obtained from spent motor oil by thermal decomposition and distillation with a high content of inorganic components:
  • hydrocarbon oils used can vary greatly in their properties due to different origins. Depending on the composition of the oils and the running time, the reaction conditions must be changed frequently to achieve consistent product qualities.
  • the bed 1 with the unloaded foam ceramic absorbs substantially only the sediments, such as zinc phosphate particles, and little additional phosphorus.
  • Bed 2 with the conventional hydrodemetallization catalyst becomes relatively fast saturated by volatile phosphorus compounds and organometallic compounds.
  • the commercial hydrogenation catalyst deactivates and provides hydrogenation products that are no longer standard.
  • disturbing products appear in the wastewater, primarily phosphorus compounds, which no longer permit normal disposal.
  • the run time for the catalyst feeds is unsatisfactory and is only three months at a throughput of 2500 tons of oil per cubic meter of catalyst.
  • Example 2 With the same arrangement of the beds as in Example 1 were in the bed 2, which contained the conventional hydrodemetallization catalyst according to Example 1, test samples of one liter each of comparative materials and Alkalialumosilikaten invention incorporated. These samples, like the entire demetallization catalyst, were passed through by the hydrocarbon oil throughout the life of the catalyst and, after completion of the operation, were removed with the demetallization catalyst and analyzed by X-ray fluorescence analysis.
  • Samples A and B are not according to the invention; the samples C and D are additionally loaded with alkali and according to the invention.
  • the analysis results of the four samples A to D, after the removal and after screening of the dust deposited in the void volumes, are summarized in Table 1 in comparison with the composition of the fresh samples.
  • the alkali loading of the aluminosilicate foam ceramic can significantly increase the effectiveness of the material for absorbing phosphorus.
  • Sample A contains only a few native alkali oxides. Their pores apparently absorb only finely dispersed, agglomerated zinc-phosphorus compounds adsorptively in the oil.
  • the aluminosilicate foam ceramic C which is additionally loaded with alkali, and especially the alkali aluminosilicate foam ceramic D, which is additionally loaded with hydrogenation metal compounds, show an even substantially increased uptake of phosphorus.
  • the lubricating oil additive zinc dialkyldithiophosphate is decomposed, with zinc forming an inorganic compound with phosphorus in which zinc and phosphorus are in the atomic ratio of 1: 1.
  • Zinc and phosphorus are then insoluble in the oil and are deposited as a zinc-phosphorus compound, mainly as zinc phosphate, in the catalyst.
  • decomposition of the additive results in further phosphorus compounds which contain no zinc. The latter have not yet been sufficiently absorbed by the previously known demetallizing catalysts and, after the hydrogenation catalysts are saturated with phosphorus, migrate with the oil through the reactor and finally appear in the hydrogenation product.
  • the alkali metal aluminosilicate can chemically bind these free phosphorus compounds.
  • the hydrogenation metal-loaded alkali metal aluminosilicate functions as a catalyst for the decomposition of organometallic compounds, for.
  • organometallic compounds for.
  • lead, iron and copper As the lead, iron and copper.
  • these metals remain as sulfides or phosphides and are fixed and collected in the large pores of the alkali aluminosilicate foamed ceramic.
  • additional zinc is deposited as a fixed compound, which presumably also previously existed as an organometallic compound in the hydrocarbon oil.
  • the expansion samples from example 2 were freed of dust by screening.
  • the arsenic contents of the dismantled demetallisation catalyst, the dust deposited in the void volume of the catalyst bed and the alkali metal aluminosilicates C and D were determined exactly in mg As / kg (ppm), based on the Ausbaumasse. Thereby, the values obtained in Table 2 were obtained.
  • the hydrogenation metal-loaded alkali aluminosilicate foam ceramic D used according to the invention is capable of taking up five times more arsenic than a conventional demetallization catalyst.
  • Table 2 Contents of arsenic in mg / kg of original finishing material after use according to Example 2 Conventional Demetallizing Catalyst 115 Foam ceramic sample A 5 Foam ceramic sample C 97 Foam ceramic sample D 581 dust ⁇ 17
  • Example 4 While in the prior art arrangement in Example 1 using the conventional demetallization catalyst only a running time of three months and a throughput of 2500 tons of oil per m 3 of catalyst are achieved, in the first experiment of Example 4 a running time of about 5 months and achieved a throughput of 4200 t of oil per m 3 of catalyst. In the second experiment of example 4, a running time of about eight months and a flow rate of 6700 t of oil per m 3 of catalyst is achieved. This achieves a significant extension of the transit time and throughput through the use of the alkaline aluminosilicate foam ceramic according to the invention in bed 2.

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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)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP20110151377 2011-01-19 2011-01-19 Procédé de traitement par hydrogénation d'hydrocarbures fortement contaminées par des composants anorganiques Active EP2479242B1 (fr)

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EP0435310A1 (fr) 1989-12-29 1991-07-03 Leuna-Werke Ag Corps formé catalytique pour l'élimination d'impurités inorganiques
WO1999003561A1 (fr) 1997-07-18 1999-01-28 Crystaphase International, Inc. Procede de filtration et de distribution de liquide pour des reacteurs chimiques
US6306289B1 (en) * 1998-03-16 2001-10-23 Tonen Corporation Catalyst for hydrogenation treatment and method for hydrogenation treatment of hydrocarbon oil
DE10134524A1 (de) 2001-07-16 2003-02-06 Sueddeutsche Benda Verwaltungs Schaumkeramik mit gerichteter offener Porenstruktur
US6759364B2 (en) 2001-12-17 2004-07-06 Shell Oil Company Arsenic removal catalyst and method for making same
WO2004101713A1 (fr) 2003-05-16 2004-11-25 Albemarle Netherlands B.V. Procede et catalyseur permettant d'eliminer l'arsenic et un ou plusieurs autres composes metalliques d'une charge d'hydrocarbures
DE102007011471A1 (de) 2006-03-09 2007-09-13 Shell Internationale Research Maatschappij B.V. Katalysatorkombination für die hydrierende Verarbeitung von Vakuumgasölen und/oder Visbreakergasölen
DE102008022098A1 (de) 2007-06-29 2009-01-02 Uop Llc, Des Plaines Verbessertes Verfahren zur Veredelung von verunreinigten Kohlenwasserstoffen

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