DE3246680A1 - METHOD FOR HYDRO-METALIZING A LIQUID HYDROCARBON MATERIAL - Google Patents

Description

A *

Process for hydrodetallization of a liquid hydrocarbon material

The invention relates to catalytic hydrodemetallization of hydrocarbon oils / especially liquid petroleum residues or shale oils / which contain significant amounts of dissolved metals and sulfur. 5

The atmospheric distillation or vacuum distillation of crude oil provides a residue (soil residue) that contains significant amounts of asphaltenes and other coal. Hydrogen that boil above about 315 ⁰ C (600 ⁰ P) contains sulfur as well as dissolved metal contaminants, similarly shale oil contains high boiling hydrocarbons and often significant amounts of dissolved metals. It is important to further process the hydrocarbon content of the residual by converting its high boiling materials to economically attractive lower boiling hydrocarbon materials. Shale oil is also processed further to maximize its yield of the desired low boiling point materials. US Pat. No. 3,558,474 describes a representative process which, when carried out, slurries vanadium sulfide in a heavy residue, followed by heating in the presence of hydrogen. In carrying out this process, the catalyst causes three reactions, first it reacts or physically absorbs the metals and other impurities, second, it catalyzes the conversion of sulfur to hydrogen sulfide, and third, it effects the desired hydrocarbon conversions. This one-step procedure

however, has significant disadvantages. The metal impurities tend to deactivate the active. vity of the catalyst in relation to the other two reactions / and the sulfur impurities tend to be deactivated the activity of the catalyst for the hydrocarbon conversion reactions. To counter this, one must increase the reaction temperature, which leads to yield losses, or large excesses of relatively expensive Use a catalyst.

It has been recognized that it is advantageous to carry out these reactions separately. Hastings et al. describe in her article "Demetallization Cuts Desulfurization Costs" in The Oil and Gas Journal, June 30, 1975 on the pages 122-130 that good results are obtained when a three-step process from demetalization, subsequent Desulfurization and subsequent hydrocarbon conversion is carried out. Similar teaching is found in U.S. Patents 3,767,569 and 3,975,259. These describe the simultaneous demetallization and desulfurization of residues, while US Pat. No. 3,841,996 contains a recycle process for the catalytic hydrofluorization and hydrocracking of a residue. The last-mentioned US-PS proposes a pretreatment for the ■ removal of metals, this pretreatment takes place but only optionally in such a way that the demetallization is optionally carried out in the circulation system. U.S. Patents 3,975,259 and 4,214,997 describe the use of slurries of catalyst particles, in particular Slurries of colloidal catalyst particles, to carry out various hydroprocessing reactions. These colloidal particles are natural only

very difficult to remove from the reaction product.

When carrying out a decontamination reaction, like a hydrodetallization, offers a batch process or a fixed bed process with a disabled Flow (fixed bed plug-flow process) advantages .. This lies in the implementation of these two processes End product in the form of a largely decontaminated material in the reaction zone. In the case of one continuously working backmixing reaction zone equipped with a stirrer, the end product is only in the form of an equilibrium product, with newly added contaminated feed containing the decontaminated reaction product is in balance. This is of course inconvenient in those situations where the not removed Metal deactivate the catalysts for the desulfurization reaction and / or the hydrocarbon conversion reaction can. The batch process is of no interest with regard to the possible throughputs in a large refinery. Similarly, constrained flow fixed bed processes are useful for treating crude residues not useful, because the front end of the bed quickly with metals, sulfur, coke, salts or the like Clogs solids found in or formed in these still bottoms.

The object of the invention is to create an improved catalytic hydrodetallization process for Processing of petroleum materials contaminated with metals including petroleum residues and shale oils, which is capable of (a) efficiently removing metals down to low levels, (b) a continuous one Allow procedure and (c) a simple isolation of the demetallized product from the Allow demetallization catalyst.

This object is achieved by the invention according to the patent claim.

The invention provides a process for catalytic hydrodemetallization of a crude oil material selected from shale oils and residua that include a substantial amount of material boiling above 315 ° C (600 ⁰ F) and further comprises from 0.5 to 10 wt .-% is accordingly organic Sulfur and 20 to 2000 ppm (by weight) metals. This process consists in treating the starting material with gaseous hydrogen in an amount that is minimally above the saturation amount, and a solid demetallization catalyst, which can be characterized as microporous and a uniform between 0.05 and 0.3 mm (50 to 300 mesh) lying particle size, to mix to form a triple slurry, to send the slurry in a stirred state through an elongated tubular reaction zone which is provided with internal cracks (plug flow) and is designed such that a slurry velocity between 0.3 and 4, 5 m / s (1.0 to 15 ft / sec) is achieved, this slurry rate being sufficient to keep the solid catalyst particles in suspension and an average slurry residence time in the reaction zone of 1.5 to 15 minutes at a temperature of 400 to Maintain 48O ⁰ C (750 to 900 ⁰ F). The effluent from the reaction zone is separated into a solid-catalyst-containing phase and a solid-catalyst-free demetallized product phase.

When carrying out the method according to the invention

the metal content of the material is reduced by a factor of at least 5 from the original value of 20 to 2000 ppm (based on weight) to 0 to 40 ppm (based on weight).
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The invention is explained in more detail by means of the accompanying drawings. Show it:

Fig. 1 is a graphic representation of the activity of 2 hydro. demetallization catalysts as a function of time;

Fig. 2 is a flow diagram of a hydrodemetallizing process according to the invention;

3 shows, partly in section, another reactor configuration which is used for carrying out the inventive Process is suitable.

Hydrocarbon feedstocks that are advantageous in Way to be treated by the method according to the invention can contain significant amounts of metals, for example 20 to 2000 ppm (based on weight) metals, preferably 75 to 1500 ppm (based on weight) Metals and especially 100 to 1000 ppm (by weight) metals. These metals are generally as organo-metallic compounds soluble in the hydrocarbon feed. The present metals exist generally primarily composed of nickel and vanadium, but it can also be, for example, iron, copper and Trade arsenic. The amounts and proportions of the metals vary depending on the type of hydrocarbon starting material. If the starting material is a petroleum residue, then it contains nickel and vanadium as the main

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metal! impurities / with these materials in abundance from 50 to 2000 ppm (based on weight) and in particular in amounts from 75 to 1500 ppm (based on the weight) are available. Is the source material a. Shale oil / then arsenic is the most common pollution and is in amounts from 20 to about 200 ppm (by weight) and especially in amounts from 20 to 150 ppm (based on weight).

According to a first embodiment, the starting material used consists of an atmospheric petroleum residue or a vacuum petroleum residue, ie it is the bottom product of an atmospheric distillation or a vacuum distillation of a crude oil. Such materials are characterized in that they contain in a substantial amount of material boiling above 315 ° C (600 ⁰ F) and also substantial amounts of organic sulfur, such as 0.5 to 10 wt .-%, of. These petroleum residues, which are used as starting materials, may optionally have been processed beforehand, for example they may have been washed to remove salts.

The residue feed materials may be previously subjected to a deasphalting treatment. Without one such treatment may contain up to 50 percent by volume asphaltins.

The feed materials are previously subjected to a deasphalting treatment subjected, for example, a solvent deasphalting, such as. B. a propane deasphalting, then their asphalt content can increase in general

considerably less than 10 percent by volume and often reduced to practically zero. The deasphalting however, does not set the level of metal impurities in the deasphalted oil to appropriate levels down.

Examples of suitable feed materials are the 315 ° C (600 ° F) + residuals and shale oils shown in the table I are summarized. In Table I, representative metal contents are also listed, as they are in general can be found in each of these feed materials.

Table I.

Charging material and specific ■ weight, ° API _____

Metal content, ppm based

on weight

. Nickel plus other BeVanadin components

Vacuum residual of an Arabian Heavy Crude Oil, 4.6 °

Vacuum residual of a Venezuelan Crude Oil, 10.9 °

Vacuum residual of California Crude Oil, 5.4 °
Vacuum residual of an Iranian Heavy Crude Oil, 6.3 °

Atmospheric residual of an Iranian Heavy Crude Oil, 14.4 °

Atmospheric residual of an Arabian Heavy Crude Oil, 11.5 °

Slate! I, 18.8-19.7 ° Shale Oil II, 20.2 °

220

666

294

462

224

124

28 Arsenic 33 Arsenic

BATH ORIGINAL

The catalyst used to carry out the hydrent ¹ metallization reaction according to the invention is a solid material in the form of individual particles. The particle size should be uniformly within a range of 0.05 and 0.30 mm (50 to 300 mesh), that is, the catalyst particles pass evenly through a sieve with a mesh size of 0.30 mm and on a sieve with a clear mesh size Mesh size of 0.05 mm should be retained. Preferably the particles are uniform particles within a range of 0.05 to 0.20 mm, and more preferably 0.07 to 0.15 mm (70 to 250 mesh and 100 to 200 mesh, respectively). Catalyst particles within this range are advantageous in that they are small enough to be suspended and slurry in the hydrocarbon feedstock to be treated, but large enough to be completely removed from the treated product by conventional centrifugation , Filtration or the like. Can be recovered. Furthermore, this particle size offers advantages in that the particles can be produced in an inexpensive manner by spray drying methods, that they have large surface area: mass ratios and enable very high degrees of metal absorption. Levels of up to 50 to 150% of the original catalyst weight can be detected. In addition, catalyst particles of this size are more effective in hydrogen utilization than the larger particles required in fixed bed demetallation systems.

The uniformly sized particles are preferred microporous. In the case of larger particles, for example

BATH ORIGINAL

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As pellets of 1.3 to 3.0 mm (4 to 16 mesh) in size, there is often a need for a macroporous structure, which is not required here. The catalyst advantageously has an internal surface area of at least 100 m ² / g and preferably 200 to 1500 m ² / g and, in a very particularly preferred manner, between 300 and 1200 mVg.

Two general classes of catalysts are suitably used. The first class consists of deposited on a carrier, made of base heavy metals existing sorption catalysts, the. Support can consist of any inert support, for example an organic oxide or a silicic acid-like carrier or activated carbon or the like., With the desired Metals are deposited on the surface. Such carriers consist, for example, of aluminum oxide, Silica-alumina, silica-magnesia, silica-boron oxide, titanium oxide, zirconium oxide and activated carbon. The metals can be selected from groups VI and VIII of the Periodic Table of the Elements are and consist for example of nickel, tungsten, molybdenum, cobalt or the like. Or mixtures thereof. iron and vanadium are also suitable metals. The Metal-Ie are generally in the form of oxides or sulfides. Conventionally known supported hydroprocessing catalysts, like NiMo, NiW, CoMo or CoW on aluminum oxide or silicon dioxide-aluminum oxide or Activated charcoal can be used. Other examples of supported metal catalysts are NiFe, NiCo or NiV. The amount of metal on the catalyst need not be high. Amounts of metal of 1% or less, based on the total catalyst weight

BATH ORIGINAL

good results. Even if amounts of up to 10 or 15
% By weight or more can be used and fall within the scope of the invention / so the use of such amounts offers no advantages / but is even rather
disadvantageous with regard to the higher costs and the lower demetallization capacity.

The second type of catalyst that is used to carry out
of the method according to the invention is suitable, consists

made of non-metallic sorption catalysts with a
large surface. These catalysts can be made from
Above mentioned supports exist, on the surface of which no metals are deliberately deposited. These
Materials are effective for the demetallization reaction. It is believed with certainty that these materials
work according to a self-catalysis process. they show
initially a low demetallization activity,
however, after absorbing small amounts of metal, their activity increases. This catalyst activity-time relationship is shown graphically from FIG. 1,

which is the extent of absorption of metal from a metal-containing petroleum feed as a function the time in the case of two catalysts. The first catalyst, namely Catalyst A, is a

metal-containing catalyst deposited on a carrier. As can be seen, it shows an initial one
high activity, which gradually declines in the course of use, with poisoning and loading with the metal from the starting material. The second catalyst, Catalyst B, is a metal-free catalyst. He only has a low initial
Activity that increases with metal deposition. After this

a substantial loading, for example to the extent of 1%, has been achieved, this material begins as a previously loaded catalyst to act and shows a gradual decrease in activity over the course of its on-set.

Catalysts used in accordance with the invention are preferred those microporous catalysts based on activated carbon, alumina or alumina-silica, which may contain added metals. Activated carbon based catalysts are most preferred. Activated carbon offers considerable cost advantages. It is cheap in itself and allows cheap reclamation of metals by combustion. Particularly preferred catalysts consist of activated carbon without any added Metal as well as activated carbon, which carries up to 1% by weight CoMo, CoW, NiW, NiMo or NiV.

2 shows a flow diagram of the process according to the invention, according to which a hydrocarbon charge, in this case an Arabian heavy oil residue, which contains 250 ppm of metals and 5% by weight of sulfur and has optionally previously been desalted and / or deasphalted, is passed through the hydrodetallization unit Line 11 and is fed by means of the pump 12. Fresh catalyst in the form of individual particles is fed to the oil starting material through line 14. The catalyst is an activated carbon with a particle size of 0.07 to 0.15 mm and a mean pore diameter of approximately 4.0 nm and a surface area of 500 to 750 m ² / g. The make-up catalyst is used in an amount of approximately 0.071 to 1.42 liters, and preferably approximately

from about 0.042 to about 0.071 liters, and especially 0.283 liters, per barrel of the oil feedstock (0.0025 to 0.05, 0.005 to 0.0025 and 0.01 cubic feet per barrel, respectively). The solid catalyst is fed through catalyst feed funnels 15 and 16, one of which is closed and is filled via the catalyst feed line 17, while the other feeds the line 14. The feed hopper that is in use is under increased pressure so that the feed material is not blown back. The pressure is expediently maintained by hydrogen which is generated from the hydrogen feed line 19 through the catalyst feed hopper pressure line 20. The resulting oil / catalyst slurry travels through line 21, is mixed with approximately 2/3 barrels per barrel of recycle catalyst slurry fed via line 41 to form a usually two phase reactor feed slurry which itself is approximately 1/3 8 to 1/2 and in particular 1/6 to 2/5 and preferably about 1/3 volume of solid catalyst and the remainder of liquid oil, mixed. This corresponds to a solid: liquid: starting material volume ratio of 1: 7 to 1: 1 and in particular 1: 5 to 2: 3 and preferably approximately 1: 2. This mixture is pumped through the slurry pump 22, with further hydrogen (up to a total of added hydrogen of about 7080 to 42480 and especially 14150 1 / barrel of the oil feed) supplied via line 19 to produce the required three phase pesticide liquid -Gas slurry mixed and heated to about 400 to 480 ⁰ C and preferably about 430 to 480 ⁰ C and iris especially about 440 ⁰ C in the feed heater 24

heats. The heated mixture is continuously fed to the elongated tubular reactor 25 via line 26 supplied under a pressure of about 73 to 201 atmospheres and preferably 110 to 183 atmospheres. The length of the reactor 25 is sized so that an average slurry residence time of about 1.5 to about 15 minutes, and preferably about 2.5 to about 10 minutes. The diameters of the pipes in the Reactor 25 is sized to have a moderate linear slurry velocity of 0.3 to 4.5 m / s and preferably 0.6 to 3.0 m / s is maintained. Such Velocities are high enough to keep particle sedimentation to a minimum, however low enough to prevent reactor wall erosion and catalyst decomposition to keep fine particles to a minimum. The metals in the feed are on the Catalyst absorbed in the reactor 25. As can be seen from Fig. 3, the reactor 25 can be various static or active mixing devices to favor a card catalyst dispersion and a hydrogen dissolution in the Have charge material. The demetallized product is discharged from reactor 25 through line 26 to the precipitation vessel 27 fed in, in which residual hydrogen is removed and drawn off overhead via line 29, The amount of residual hydrogen can be small since the amount originally added is generally such is controlled so that it does not significantly exceed requirements. This is done for two reasons, firstly to keep losses to a minimum and, secondly, to ensure maximum liquid filling in the reactors. The excess hydrogen can be discarded, but is either recycled or used for further use Processing purposes used. The soil product in

the failure device consists of a slurry of demetallized oil and catalyst and is fed through line 30 to the catalyst separation hydroclone 31. In the hydroclone 31 there is a light phase of oil and up to about 100 ppm (by weight) kata lysator fed through the line 32 to the filter 34, where the remaining catalyst is separated and an im leaving substantially catalyst-free demetallized (usually less than 20 ppm metal) oil product filtrate; that is withdrawn through line 35 and usually to further hydroprocessing such as hydrodesulphurisation or hydroconversion in a known manner. The heavy product formed in the hydroclone 31 is a catalyst-enriched product that is withdrawn through line 36 and a second hydroclone 37 is supplied. In the hydroclone 37, the catalyst-enriched product is converted into a hydrocarbon-rich fraction which is transferred to line 26 via line 39 is fed, and in a catalyst concentrate fraction, which is withdrawn through line 41 and fed to line 21 is separated. A portion of the catalyst concentrate fraction is taken from line 41 through line 42 removed, combined with the catalyst recovered in the filter 34, which is fed through the line 44, and fed to the decanter 45 in which approximately 0.071 to about 1.42 liters of catalyst per barrel of oil feedstock withdrawn through line 46 and, if necessary, used, but preferably for recovery the metal content can be treated by measures not shown. The liquid phase that is in the decanter 45 occurs, the loading line 11 is through the line 47 and the recycling pump 49 are fed.

The catalyst particles 0.05 to 0.3 in size mm allow the convenient use of a variety of alternative solid / liquid separation devices for Catalyst recovery, for example the use of simple filters, settling devices or the like. These units can be replaced by other units or measures without departing from the invention. In a similar way Corresponding ones can then be used if other metal-contaminated feed materials are used Changes in working conditions are carried out.

For example, when a shale oil containing 20 to 100 ppm arsenic is processed, the reaction ^{temperature can be in the range between 400 and 480 °} C., but pressures of 7 to 146 atmospheres and residence times of 1.5-5 minutes are preferred will.

Figure 3 shows a reactor design which is an alternative represents the embodiment shown in FIG.

The reactor 50 of FIG. 3 can be used in the process according to Fig. 2 can be integrated as a replacement for the reactor 25. The reactor 50 is fed via line 51 with a slurry of metal containing hydrocarbon oil feedstock, Catalyst and hydrogen charged. The catalyst: oil ratio corresponds to that described above, while the hydrogen: oil ratio is lower. The slurry is through the elongated reaction tubes 52, 52a, 52b, etc. sent, these tubes are dimensioned such that the im

In connection with the description of FIG. 2 specified speeds and residence times are observed.

An internal mixer 54 is located in the pipe 52b. This is so placed that it can be replaced periodically can if due to an excessive load it blocks the slurry stream begins to constrict. The tubes 52 etc. are horizontal. In Fig. 2 a vertical pipe arrangement was shown. Either arrangement works satisfactorily, but the horizontal pipe arrangement of FIG Preference is given because it maximizes the amount of liquid filling the reactor and creates gas vacancies keeps to a minimum. Another help in preventing gas vacancies is phased hydrogen addition through the hydrogen inlets 55 and 55a, which are supplied through the feed line 56. The gradual addition of hydrogen enables this to be maintained the desired saturation of the liquid with hydrogen in the reactor without this being significant Excess must be added in early reaction stages. The entire hydrogen: oil charge is similar to that according to FIG. 2.

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Claims (14)

Patent Attorneys ■ European Patent Attorneys Dr. Müllcr-Bore and Partner POB 880720 - D-8000 Munich 88 «Br. W. Müller-Bore t Dr. Paul Deufel Dipl.-Chem., Dipl.-Wirtsch.-Ing. Dr. Alfred Schön Dipl.-Chem. Werner Hertel Dipl.-Phys. Dietrich Lewald Dipl.-Ing. Dr.-Ing. Dieter Otto Dipl.-Ing. C 3394 Chevron Research Company 525 Market Street San Francisco, CA 94105 / USA Process for hydrodemetallizing a liquid hydrocarbon material Claims 10 / 1.! Process for hydrodemetallization of a liquid Hydrocarbon material / that is 20 to 2000 ppm by weight, contains dissolved metals, characterized in that a) the material with gaseous hydrogen in one with respect to the saturation excess amount and a solid demetallization catalyst which is microporous and has a particle size of 0.05 to 0.3 mm (50-300 mesh) to form a Three phase slurry is mixed, b) Pass the slurry through an elongated tubular reaction zone setting a slurry velocity of 0/3 to 4.5 m / s (1-15 ft./sec.) and an average residence time in the reaction zone of 1/5 to 10 minutes is sent at a temperature of 400 to 480 ⁰ C (750 to 900 ⁰ F) to deposit at least a portion of the metals on the solid demetallization catalyst to form a demetallized hydrocarbon slurry 10. and c) the demetallized hydrocarbon slurry removed from the slurry zone and from the demetallized hydrocarbon slurry a demetallized hydrocarbon that is free of demetallization catalyst is obtained will. 2. The method according to claim 1 / characterized in that the solid catalyst is used in a volume ratio to the hydrocarbon material of 1: 1 to 1: 7 will. 3 '. The method of claim 2 characterized in that the passage through an elongated tubular reactor is under a hydrogen pressure of 73 to 201 atmospheres (1000 to 2750 psig). 4. The method according to claim 3 / characterized in that the hydrocarbon material used is a petroleum residue and the metals are nickel and vanadium exist. 5. The method according to claim 4, characterized in that that the reaction zone is a horizontal reaction zone. . 6. The method according to claim 4, characterized in that the solid demetallization catalyst used consists of inorganic oxidic or silicic acid-containing materials or activated carbon with a surface area of at least 100 m ² / g. 10 7. The method according to claim 6, characterized in that the catalyst used additionally contains a base metal. 8. The method according to claim 6, characterized in that the catalyst used contains activated carbon. 9. The method according to claim 8, characterized in that the catalyst used is one or more metals, selected from nickel, vanadium, cobalt and tungsten, contains, 10. The method according to claim 8, characterized in that the catalyst used consists essentially of activated carbon. 11. The method according to claim 9 or 10, characterized in that the liquid hydrocarbon material used consists of a petroleum residue. 12. The method according to claim 11, characterized in that a hydrogen pressure of 110 to 183 atmospheres (1500 to 2500 psig), a temperature of 430 to 480 ⁰ C (800 to 900 ^° F), a dwell time of 2.5 to 10 minutes, and a slurry speed of 0.6 to 3.0 m / s (2 to 10 ft / sec.) Must be maintained. 13. The method according to claim 9 or 10, characterized in that that the liquid hydrocarbon material used consists of a shale oil. 14. The method according to claim 13, characterized in that a hydrogen pressure of 73 to 146 atmospheres (1000 to 2000 psig), a temperature of 430 to 480 ^e C (800 to 900 ⁰ F), a mean residence time of 1.5 to 5 min and a slurry velocity of 0.6 to 3.0 m / s (2 to 10 ft./see.) must be maintained.