EP2479242A1 - Method for hydroprocessing of hydrocarbon compounds heavily contaminated with inorganic substances - Google Patents

Abstract

Deposition of sediments and catalyst toxins, preferably with inorganic components in contaminated hydrocarbons comprise hydrogenated processing of the contaminated hydrocarbons in a fixed bed reactor. The fixed bed reactor comprises alumina, silicon dioxide and elements of the 1st main group as main components, and is loaded optionally with hydrogenation component. The contaminated hydrocarbon is led over a bed of solid particles from a combination of adsorbent and catalyst, which comprises the super macroporous alkali aluminosilicate with pores of 0.01-3 mm diameter.

Description

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. Typically, 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. There is a wide range of recyclable contaminated oils such as hydraulic fluids, heat transfer media, engine lubricants and cutting oils that could be reusable. Pyrolysis oil is formed by rapidly heating materials in an oxygen environment to form hydrocarbon-containing fluid. When 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.

Such hydrocarbon streams contaminated with inorganic ingredients and heteroatom compounds are detrimental to catalysts and equipment used in hydroprocessing of the hydrocarbons. They clog the catalyst bed and poison the catalysts. Therefore, there is a great need for materials that can absorb catalyst poisons and debris and protect the main catalyst from these harmful substances.

From the US 7,638,040 and the corresponding DE 10 2008 022 098 A1 discloses a process for recovering hydrocarbons from contaminated hydrocarbons for commercial use in lubricants, solvents and fuels. Contaminated hydrocarbons contain non-distillable components, such as Example high molecular weight hydrogen-poor hydrocarbons, metal compounds and solids that are detrimental to the use of these oils in the hydrogenation process. Most of the contaminants are separated by contacting the contaminated hydrocarbons with a stream of hot hydrogen gas, with at least a portion of the hydrocarbon components suddenly evaporating from the contaminated hydrocarbons. 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. In another embodiment, 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. It is further contemplated that 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.

• Verstopfung des Katalysatorbetts mit anorganischen Sedimenten, die zu einem hohen Differenzdruck, zum vorzeitigem Abstellen der Anlage und zum Wechsel der Reaktorbefüllungen führen,
• Vergiftung der Hydrierkatalysatoren durch die anorganischen Inhaltstoffe, wie Phosphor, Arsen, Blei und weitere Metalle,
• Austreten von anorganischen Produkten, wenn sie die Katalysatorschichten durchlaufen und Übergang in das Abwasser, das dadurch mit erhöhten Konzentrationen schädlicher Substanzen kontaminiert wird und nicht auf normalem Wege entsorgt werden kann,
• schließlich Minderung der Produktqualitäten durch das Nachlassen der Katalysatoraktivität

However, the known hydrodemetallization catalysts allow only short periods of technical equipment of, for example, only one month, when the non-organic contents of the contaminated oils, such as sediments and compounds of phosphorus and / or arsenic, are so high that they are used for rapid deactivation of the Hydrodemetallisierungskatalysators in the first reactor and the hydrotreating catalyst in the second reactor lead. The inorganic ingredients trigger severe obstructions in plant operation. Such serious disadvantages are:

• Clogging of the catalyst bed with inorganic sediments leading to high differential pressure, premature shutdown of the plant and reactor changes
• Poisoning of the hydrogenation catalysts by the inorganic ingredients, such as phosphorus, arsenic, lead and other metals,
• Leakage of inorganic products as they pass through the catalyst layers and transfer to the wastewater, which is thereby contaminated with increased concentrations of harmful substances and can not be disposed of normally;
• finally, diminution of product qualities due to the cessation of catalyst activity

For trapping inorganic impurities from sulfur-containing hydrocarbon streams Demetallisierungskatalysatoren as a shaped catalyst body based on alumina or aluminosilicate as a carrier, for example according to the EP 0435310 A , used which contain nickel and / or cobalt in combination with molybdenum or tungsten compounds. The hydrogenation components are present in the reaction atmosphere in the form of Ni ₃ S ₂ or Co ₉ S ₈ and MoS ₂ or WS ₂ . To increase the uptake of dirt or inorganic fine particles, the void volume is increased by profiling the catalyst moldings, for example by using a ring profile or a three-armed profile, which is rotated about the longitudinal axis. To trap the catalyst poison arsenic from organo-arsenic compounds, high nickel compositions are used to bind arsenic as NiAs. The pore sizes of the catalysts are 15 to 100 nm.

Similar compositions, specific surface areas and pore sizes are used for the removal of contaminants, for example in U.S. Pat WO 2004/101713 and in the US 6,759,364 called. These hydrogenation catalysts derived from the usual sulfur-fixed hydrorefining catalysts have specific surface areas of more than 10 m ² / g, usually between 150 and 300 m ² / g, and are therefore too porous to collect large quantities of inorganic material in their interior. They also absorb relatively little phosphorus from volatile phosphorus compounds.

When using such catalysts for the hydroprocessing of oils containing high amounts of organic phosphorus compounds and organically bound metals, they are not retained sufficiently long before the actual hydrogenation catalyst. The hydrogenation catalyst is rapidly poisoned, deactivated and does not achieve sufficiently long runtimes. The change of expensive catalyst fillings is due in a relatively short time.

From the US 7,638,455 B2 and the corresponding DE 10 2007 011 471 discloses a catalyst combination for hydroprocessing contaminated hydrocarbon oils using a hydrodemetallization catalyst having a bimodal pore distribution in the first reaction zone. It contains pores with a diameter of 3 to 10 nm with a pore volume of 0.25 to 0.35 cm ³ / g and in addition pores with a diameter of 1000 to 10000 nm = 1.0 to 10 microns = 0.001 to 0.01 mm with a pore volume of 0.25 to 0.35 cm ³ / g. Also, 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. In addition, the material may still contain hydrogenation metal compounds. However, the catalysts described are not suitable for the absorption of dirt and catalyst poisons and not intended.

From the DE 101 34 524 A1 Alumina / silicate-based catalyst carriers are known 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.

From the WO 99/03561 A1 For example, in order to take solid particulate foreign bodies from contaminated hydrocarbon streams in a hydrofinishing plant, it is known to use 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. Thereafter, they are used to treat preferably liquid hydrocarbon fractions at temperatures between 110 and 280 ° C and 1 to 100 bar in a hydrogen atmosphere. The after the EP 0412862 Absorbent compositions prepared are capable of lowering the phosphorus content to less than 500 hours from a hydrocarbon stream containing, for example, 500 ppb of phosphorus in the form of trimethylphosphine and 500 ppm of sulfur in the form of organosulfur compounds. In the presence of higher sulfur levels and longer run times, however, this catalyst loses its activity and can absorb only little phosphorus, since the nickel is converted to nickel sulfide and nickel arsenide and then no longer represents a stable sulfur-resistant hydrogenation for the hydrogenating conversion of organophosphorus compounds.

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.

To achieve this object, according to the invention, 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. In doing so, 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.

In the alkali metal aluminosilicate used according to the invention, 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. For example, 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 nature of the loading of the solid, particulate combination of catalyst and absorbent with compounds of elements of the I. main group and the VI. Subgroup and / or VIII. Group of the PSE in composition and concentrations can be varied depending on the inorganic ingredients of the used, contaminated hydrocarbon oil.

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.

• Gesamtdruck: 5 bis 200 bar
• H2-Gehalt des KLG: 50 bis 90 Vol.-%
• Durchsatz: 3 bis 8 m³ pro kg Katalysator in der 3. Zone
• Temperaturen: 300 bis 560 °C, vorzugsweise 300 bis 360 °C

The reaction conditions in the applied, improved process are for example usual conditions, such as:

• Total pressure: 5 to 200 bar
• H2 content of KLG: 50 to 90% by volume
• Throughput: 3 to 8 m ³ per kg of catalyst in the 3rd zone
• Temperatures: 300 to 560 ° C, preferably 300 to 360 ° C.

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 Demetallisierungskatalysatoren there are therefore no restrictions by the use of larger particles of dimensions of several centimeters. In addition, 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.

In a preferred embodiment, 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. In this case, 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. However, it is also possible to use a single bed of hydrogenation-metal-loaded alkali metal aluminosilicate.

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. Furthermore, 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. On the inner surface of the large pores, 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. As soon as the large pores are filled with deposits, 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; In addition, 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.

Depending on the character of the inorganic constituents of the contaminated oils, the length of the zones can be changed accordingly to extend the running times. 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.

Examples Example 1:

• Bett 1: unbeladene, kommerziell verfügbare Alumosilikat-Schaumkeramik
• Bett 2: handelsüblicher Demetallisierungskatalysator
• Bett 3: handelsüblicher, leistungsfähiger, hydrierender Ni-Mo-Katalysator

Comparative example according to the prior art

• Bed 1: unloaded, commercially available aluminosilicate foam ceramic
• Bed 2: commercial demetallizing catalyst
• Bed 3: commercial, high performance, hydrogenating Ni-Mo catalyst

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:

• Dichte (bei 15°C): 850 bis 900 kg/m³
• Siedebereich: 100 bis 550°C
• Metallgehalt: 2 bis10 mg/kg
• Phosphorgehalt: 10 bis 50 mg/kg
• Schwefelgehalt: 0,2 - 0,8 Masse-%
• Wassergehalt: < 15 Masse-%

Properties of the oil fraction:

• Density (at 15 ° C): 850 to 900 kg / m ³
• Boiling range: 100 to 550 ° C
• Metal content: 2 to 10 mg / kg
• Phosphorus content: 10 to 50 mg / kg
• Sulfur content: 0.2 - 0.8 mass%
• Water content: <15% by mass

• Gesamtdruck: 40 bis 100 bar
• H₂-Gehalt: 50 bis 90 Volumen-%
• Temperaturen: 300°C bis 500°C
• Durchsatz: 0,4 bis 1,0 Vol./ Vol.* h, bezogen auf alle drei Betten

Operating conditions:

• Total pressure: 40 to 100 bar
• H ₂ content: 50 to 90% by volume
• Temperatures: 300 ° C to 500 ° C
• Throughput: 0.4 to 1.0 vol./vol. * H, based on all three beds

• Metallgehalt: < 0,5 mg/kg (kleiner Nachweisgrenze)
• Phosphorgehalt: < 0,5 mg/kg (kleiner Nachweisgrenze)

Products according to bed 2:

• Metal content: <0.5 mg / kg (small detection limit)
• Phosphorus content: <0.5 mg / kg (small detection limit)

The 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. Subsequently, the commercial hydrogenation catalyst deactivates and provides hydrogenation products that are no longer standard. In addition, 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.

To prepare the samples of alkali metal aluminosilicate, a commercially available foamed ceramic having the following properties was modified by loading of alkali and hydrogenation components.

Properties of commercially available, low-alkali foam ceramics:
Composition in% by mass, based on anhydrous substance, see Table 1, Sample 1, fresh shape Cuboid with edge lengths 2 x 2 x 5 cm Accessible pore volume 0.9 cm ³ / g Pore diameter distribution 100 to 300 μm 20% of the pore volume 300 to 800 μm 50% of the pore volume 800 to 2000 μm 30% of the pore volume particle 0.75 g / cm ³ charge density 440 kg / m ³ specific surface 1 m ² / g

1. A) Unbehandelte, kommerziell verfügbare, alkaliarme Schaumkeramik mit oben genannter Zusammensetzung
2. B) Kommerziell verfügbare, alkaliarme Alumosilikat-Schaumkeramik mit 3 % NiO + 9 % MoO₃ beladen
3. C) Kommerzielle Schaumkeramik, mit 10 % Na₂O beladen
4. D) Kommerzielle Schaumkeramik, wie oben angegeben, mit 5 % Na₂O und 3 % NiO + 9 % MoO₃ beladen

The following samples were prepared on the basis of the above-mentioned foamed ceramic and incorporated into the 2nd bed of the hydrogenation plant:

1. A) Untreated, commercially available, low-alkali foam ceramic with the above-mentioned composition
2. B) Commercially available, low-alkali aluminosilicate foam ceramic loaded with 3% NiO + 9% MoO ₃
3. C) Commercial foam ceramics, loaded with 10% Na ₂ O.
4. D) Commercial foam ceramics, as indicated above, loaded with 5% Na ₂ O and 3% NiO + 9% MoO ₃

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.

It turns out that 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. On the other hand, 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.

Obviously, in the workup and hydrogenation process, 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. In addition, however, 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. However, the alkali metal aluminosilicate can chemically bind these free phosphorus compounds.

In addition, the hydrogenation metal-loaded alkali metal aluminosilicate functions as a catalyst for the decomposition of organometallic compounds, for. As the lead, iron and copper. After hydrogenating catalytic decomposition, these metals remain as sulfides or phosphides and are fixed and collected in the large pores of the alkali aluminosilicate foamed ceramic. Furthermore, additional zinc is deposited as a fixed compound, which presumably also previously existed as an organometallic compound in the hydrocarbon oil.

All of these inorganic substances are collected by the Alkalialumosilikat materials before the actual hydrogenation catalyst and protect the latter from premature poisoning. Thus, the quality characteristics of the oil can be fulfilled over a much longer time. <b> Table 1 </ b>: Composition of the developed conventional demetallization catalyst and the built-in samples according to Example 2 Composition in% by mass, based only on inorganic constituents, calculated as oxides ingredients Demetallizing catalyst fresh Used Demetalli-sierungskatalysator Sample A Sample A Sample B Sample B Sample C Sample C Sample D Sample D fresh gebr. fresh gebr. fresh gebr. fresh gebr. SiO2 66.3 55.4 58.4 46.0 59.2 37.7 55 25.5 Al2O3 26.9 22.1 24.0 20.5 24.0 15.3 22 10.2 Trager component 82.0 70.8 Na2O 0.1 1.8 1.4 1.6 1.2 11.6 7.5 5 2.6 K20 4.4 3.6 3.0 2.3 3.9 2.4 3.0 1.3 CaO 0.2 0.3 0.2 1.0 0.1 0.2 0.6 1.0 2.2 NiO 3.0 2.3 3.1 1.3 MoO3 8.0 6.3 9.1 4.0 Oxidizing hydrogenation components 18.0 15.7 FeO 0.1 0.2 0.3 0.5 0.7 0.5 0.8 P2O5 10.0 15.0 16.0 0.1 32.0 44.8 ZnO 2.1 1.5 2.4 1.8 3.2 CuO 0.1 0.1 PbO 1.0 1.3 1.6 Cl 1.0 Other 0.5 1.0 1.5 0.2 0.6 0.3 0.5 total 100 99.8 100.0 99.8 100 Ingestion of inorganic substances calculated as oxides in g / 100 g cat. 14 20 25 57 125

Example 3

In this example, the inclusion of the particularly strong poisoning acting on the hydrogenation catalysts, their phosphorus-like element arsenic by means of the invention, hydrogenation-loaded alkali metal aluminosilicate foam ceramic described in more detail.

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 result shows that 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. Thus, in the inventive use of the hydrogenation metal-loaded alkali metal aluminosilicate foam ceramic, significantly better protection of the hydrogenation catalysts from arsenic poisoning is to be expected than by the use of the usual Demetallisierungskatalysatoren. 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

In this example, the advantageous results of the technical use of alkali aluminosilicate foam ceramic according to the invention by the trapping of impurities are described

• im ersten Experiment jeweils zu gleichen Volumenteilen durch die Materialien C und D gemäß Beispiel 2 ersetzt; C wird vor D angeordnet
• und in einem zweiten Experiment das gesamte Bett durch das Material D gemäß Beispiel 2 ersetzt.

In the arrangement as described in Example 1, the volume of the conventional Demetallisierungskatalysators

• replaced in the first experiment in equal parts by the materials C and D according to Example 2; C is placed before D.
• and in a second experiment, replacing the entire bed with the material D of Example 2.

Using these materials, the feed oil is enforced in both experiments as in Example 1, and the running time is determined until the hydrogenation product quality after the third bed no longer meets the quality requirements.

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.

Example 5

In a further experiment, the unloaded, commercially available aluminosilicate foam ceramic in bed 1 is replaced with a 10-mass Na ₂ O-loaded wide-pore ceramic foam and filled the entire bed 2 with the material D. Due to the further improved absorption of phosphorus, the filling time is extended to one year at a throughput of 9000 t of oil per m ^{3 of} catalyst. Thus, a commercially economically long service life of the catalysts is achieved in comparison with conventional hydrogenation plants with fixed bed reactors.

Claims (15)

Process for separating sediments and catalyst poisons from hydrocarbons contaminated in particular with inorganic constituents by hydrogenating the contaminated hydrocarbons in a fixed bed reactor, wherein
the fixed bed reactor comprises Al ₂ O ₃ , SiO ₂ and elements of main group 1 of the periodic table as main components and is optionally loaded with hydrogenation components, and
the contaminated hydrocarbon is passed over a bed of solid particles of a combination of adsorbent and catalyst containing supermacroporous alkali metal aluminosilicate having pores of 0.01 to 3 mm in diameter. A process according to claim 1, wherein an alkali aluminosilicate is used in the bed in a first zone and an alkali metal aluminosilicate loaded with a hydrogenation component in a second zone. The process of claim 1 wherein the entire bed contains particles of alkali aluminosilicate loaded with a hydrogenation component. Method according to one of claims 1 to 3, wherein the mass ratio of SiO ₂ to Al ₂ O ₃ in Alkalialumosilikat 5: 95 to 80: 20. Method according to one of claims 1 to 4, wherein as alkali constituents of the aluminosilicate compounds of elements of the 1st main group 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 used become. A process according to any one of claims 1 to 5, wherein the alkali metal aluminosilicate contains 0.1 to 30% by mass of Na ₂ O and / or K ₂ O. A process according to any one of claims 1 to 6, wherein the alkali metal aluminosilicate contains 0 to 10% by mass of an element of VI. Subgroup of the Periodic Table of the Elements and / or 0 to 10% by mass of VIII. Group of the Periodic Table of the Elements contains. Method according to one of claims 1 to 7, wherein the alkali metal aluminosilicate as elements of VI. Subgroup of the Periodic Table of the Elements 0.0 to 10 mass% of molybdenum and / or tungsten and as elements of the VIII. Group of the Periodic Table of the Elements 0.0 to 10 mass% of iron, nickel and / or cobalt. A method according to any one of claims 1 to 8, wherein the alkali metal aluminosilicate is applied in particles of 3 to 50 mm in diameter of any shape. A method according to any one of claims 1 to 9, wherein the alkali metal aluminosilicate has a pore volume of 0.6 to 1.5 cm ³ / g, which is predominantly present in pores with diameters of 0.01 to 3.0 mm. A method according to any one of claims 1 to 10, wherein the alkali metal aluminosilicate has a specific surface area of less than 10 m ² / g Method according to one of claims 1 to 11, wherein from a highly contaminated hydrocarbon oil in a first zone preferably finely divided sediments are deposited on the Alkalialumosilikat and reacted in a second zone, preferably organometallic compounds by chemical reaction on a hydrogenation metal laden alkali metal aluminosilicate and the metals in the form of chemical Compounds are held by Alkalialumosilikat. Method according to one of claims 1 to 12, wherein zinc phosphate and zinc phosphide are preferably deposited from a spent motor oil in a first zone and in a second zone preferably volatile hydrogen phosphide compounds and organophosphorus compounds are reacted by chemical reaction of a Alkalialumosilikat and the phosphorus chemically bonded by Alkalialumosilikat becomes. Method according to one of claims 1 to 13, wherein in a second zone preferably organosulfur compounds by chemical reaction on a hydrogenation metal-loaded alkali metal aluminosilicate are reacted and arsenic is chemically bound by Alkalialumosilikat. Process according to one of claims 1 to 14, wherein the alkali metal aluminosilicate in the second zone in addition to phosphorus further elements such as As, Fe, Cr, Cu, Pb, Zn, after the hydrogenating decomposition of the respective organometallic compounds in large pores in the form of fixed chemical Records connections.