DE2215520A1 - Hydro refining process - Google Patents

Description

Hydro refining process

The invention relates to hydraulic refining processes in particular processes for the catalytic conversion of petroleum residue oils with a content of impurities, those in the form of inorganic metal salts, alkalis and similar compounds exist. , _

In the reaction of hydrocarbon oils with oxidic catalysts and in particular activated metal oxides des Aluminum oxide and / or silicon dioxide containing type alone or together with other metal oxides such as thorium oxide, zirconium oxide, Titanium oxide, chromium oxide, molybdenum oxide etc. lead to impurities in the hydrocarbon feed water, which in Forir. inorganic metal salts such as halides or sulfates dos Natriun.s, or as alkalis such as lJatriunäiydroxyd may be present, to an accumulation in the reactor, so that the pressure in the reactor can rise until the reactor clogs.

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fertilize and reduce the activity of the catalyst, if necessary reduce the life of the catalytic converter or both, in any case it is an established fact that certain forms of organometallic compounds from some hydrocarbon inserts are on the catalyst precipitate, whereby the effectiveness of the catalysts is impaired.

Residual oils with a high content of metal compounds lead, in contrast to lower-boiling hydrocarbon oils lead to a significantly stronger deposition of heavy metals on the catalytic converters and thus cause increased Deactivation of the catalyst, while larger proportions of solids and salts · in the residual oils are the main cause of clogging of the reactors. Although the impurities present in various forms, are the important impurities for catalyst deactivation. in the essential as high molecular weight organometallic compounds such as metal-containing porphyrins, or other organo-metal complexes of nickel or vanadium present while clogging the reactors by in general as inorganic metal salts such as compounds present as halides or sulfates of sodium caused. The deterioration in activity, des The catalyst is permanent. The negative effects of this two types of contamination with respect to the catalyst act.

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tat must be distinguished from the inactivation that results from the accumulation of carbonaceous precipitates on the catalyst material. The catalyst activity can be temporarily real due to the formation of carbonaceous precipitates on the catalyst surface during the conversion; tion, but such precipitates can be removed in a generally usual regeneration process by incineration. The accumulation of metal impurities such as alkali salts on the catalyst surface cannot be removed again by simple regeneration processes; this is why this type of inactivation is particularly serious. If no precautionary measures are taken to prevent the deposition of inorganic compounds on the catalyst surfaces, the back pressure in the will rise. catalytic conversion zone during the catalytic. Reaction slowly until the reactor after a relatively short time such as .2Q to 90 days - depending on the implementation conditions in the reactor, the salt content of the feed and the speed of use until the reactor is completely clogged. However, such short operating times impair the economic viability of processing. >. ... ' ■

Numerous methods have already been proposed in order to To reduce the content of inorganic metal salts, such as distilling to separate the oil from the salt content or to wash the oil, if the salt is in a desalinator.

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is soluble. The distillation of the hydrocarbon feed is a relatively effective method to avoid the use of the contaminating inorganic metal salts distillation processes are proportionate, however expensive and therefore affect the overall process costs. The removal of inorganic contaminating salts by washout is limited to the use of aqueous detergents as other detergents may be effective can, but would increase the processing costs of the hydrocarbon feed too much. The washout is therefore limited to the removal of soluble compounds, but washing out generally allows such compounds to be removed Do not completely remove connections from the insert.

One way of solving the problems of clogging the reactor with inorganic metal salts and the like has been shown by restricting the clogging of the reactor essentially to the portion of the main reaction zone. In a reactor customary in the art and having a length of, for example, about 30 to 60 meters, the plugging is limited to the first meters of the reaction zone. The plug that forms generally consists of carbon-containing deposits and deposits, together with abrasion of the catalyst, which settle in the interstices of the catalyst bed so that the free substances between the individual catalyst particles are essentially in the first Yj cm to 1 Γ · 'ο tor dor Renkt.! onszono,'. «us-

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"- S -

to be filled; this' relocation of the passages is increasing rapidly from, so that after about the first 1.5 ni of the reaction zone the normal free routes are available again »To the ' enormous costs. the shutdown of a reactor due to * Plugging due to metallic impurities in the first part to avoid the reaction zone, if possible, a "protective chamber" upstream, through which the hydrocarbon return - Standing oil is used before entering the main reaction zone This protective chamber is kept under reaction temperatures and pressures, so that the Clogging deposits form, causing the nuisance of the reactor substantially reduced vn'rd. The insert can therefore are introduced into the main reaction zone without even after clogging of the main reactor occurs for longer periods of operation, since the majority of those causing the clogging Compounds from the hydrocarbon residue oil insert are already precipitated in the protective chamber Parallel arrangement of the treasure chambers becomes a continuous one Stream of the desalinated insert obtained when the metal-containing insert is introduced into a protective chamber until this Clogged, and then diverted to the next protection chamber while the first can be cleaned. The interconnection of protective chambers for the removal of metal-containing Impurities from residual oil inserts before feeding of use in the main reaction zone. is therefore an effective measure to clog and shutdown large catalytic Avoid reactors.

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With the usual petrochemisehen Umwandlungöverfahren 'takes the catalytic activity slowly during the environmental "ι setting permanently, and zvrar · among other things, due to the formation of carbonaceous deposits on the catalogs' ■ '■'■> lysatorund partly due to catalyst poisoning. This combined effect of the two reactions can be halted by tightening the reaction conditions. Since the catalytic activity slowly decreases, the temperature in the reactor is slowly increased to compensate for the loss of catalytic activity ^{by introducing the} hydrocarbon feed at constantly increasing temperatures. It follows that the temperature of a ^! Reactor at the end of an operating time is higher than at the beginning of the operating time. After a certain time, however, a regeneration of the catalyst must be carried out in any case due to the reduction in the catalyst activity. During regeneration, coke and other carbon-containing compounds that settle on the catalyst and impair its activity are removed by methods known per se, such as, for example, by oxidation and / or steam.

/ treatment removed. The regeneration can be carried out in the same reactor or in a different reactor or a cleaning zone In any case, the regenerated catalyst is then returned to the reactor. The reactor with the regenerated catalyst is then started up again initially under relatively mild conditions, and gradually worsening conditions during operation

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subject.

When the hydrocarbon residue oil insert by introducing through a protective chamber before being introduced into the main reaction zone is desalinated, the protective chamber will be clogged so that the clogging deposits must be removed. If a protective chamber becomes clogged, it must be switched off, so that it can be purified; but this is a shutdown of the reactor to clean up the catalyst in any case. On the other hand, there is the purpose of the protective chamber in protecting the reactor so that it has an extended operating life a protective chamber seems to contradict this purpose. But since the operating time of the protective chamber is also essential, the invention is based on the object of providing a method for To develop extension of the service life of the protective cabinets, the protective effect and operating time of the reactor not. may be impaired. It is desirable that the deposits form in the protective chamber; on the other hand is it is also desirable that the service life of the protective chambers is as long as possible, i.e. that the clogging of the protective chambers should also be kept to a minimum, so far this is possible with complete desalination of the feed to be introduced into the main reaction zone of the reactor.

To solve the problem, a method for catalytic Conversion of ir-it metals contaminated to hydrocarbon feed ion at temperatures below hydrocarbon conversion and - print adjacent main action zone "

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proposed that it is characterized in that to connect the Clogging of the main reaction zone

a) the hydrocarbon feed is introduced into an upstream contact zone, the
Hydrocarbon feed with a particulate
Material is brought into contact at a temperature for the formation of deposits of inorganic metal salts and only small amounts of carbon-containing compounds, but not very large amounts of carbon-containing deposits,

b) that the hydrocarbon feed flowing off from the upstream contact zone is introduced into a main reaction zone in which the flowing off feed is below
Contacting hydrocarbon conversion reaction conditions with hydrocarbon conversion catalysts,

c) that the introduction of the hydrocarbon feed into the upstream contact zone and the forwarding of the outflowing feed from the upstream
Contact zone in the main reaction zone is carried out continuously while the inorganic
Metal salts slowly accumulate on the particulate material in the upstream contact zone and the catalytic activity in the main reaction isone due to the formation of carbonaceous deposits and / or organic deposits on the catalyst

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decreases in the main reaction zone,

d) and that the temperature in the main reaction zone to maintain the catalytic activity. is slowly increased while the reaction temperature in the upstream contact zone is kept below the temperature necessary in the main extraction zone, so that after a certain time the upstream contact zone is clogged due to the formation of deposits of metals on the particulate material , while this keeps the formation of deposits of inorganic metal salts on the catalyst in the main reaction zone to a minimum. _.- ■■ "■

When carrying out the process according to the invention, the feed is essentially desalinated in a first contact zone or protective chamber, so that the hydrocarbon feedstocks used can be better preprocessed in a subsequent main reaction zone or zones (reactor or reactors) under normal hydrocarbon conversion conditions. The protective chambers contain solid, particulate contact material, usually a catalytically active material and preferably a material corresponding to the catalyst used in the main reaction zone. IM..ern k-the temperature of the protective chamber or must be sufficiently high to provide a vollatändiges in substantially Entsnkcn and preferably partially removing

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Metals. Preferably, part of the residual hydrocarbon oil feed used is converted, however, the amount of conversion must not be so great that considerable amounts of carbon-containing waste. can form storage and decomposition products.

In a preferred embodiment of the invention Procedure becomes a. Large number of protective boxes connected in series j the protective chambers contain solid particulate • catalytically active material, which on one to the partial Conversion of the hydrocarbon feed is kept at a suitable temperature. In these embodiments, a Part of the conversion of the hydrocarbon feed into protection chambers made so that the capacity of the main reactor or the main reactors can be reduced v / grounding the first of the protective chambers in a row is kept much smaller than the following chambers, so that the The first of the protective chambers can be switched off and on using a branch line for regeneration, while the subsequent treasuries to protect the reactor or the main reactors remain switched on. The use of series-connected protective chambers is therefore before a Parallel connection is preferred, especially if a partial conversion of the carbon hydrogen input has already taken place target.

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The main task of the upstream protective chamber or chambers is that the deposition of inorganic metal salts from the hydrocarbon feedstock should take place here and not in the main reactor or in the main reactors. This extends the service life of the main reactor. On the other hand, it is desirable that the operating time of the protective chamber or protective chambers should be as long as possible. Optimizing the operating time of the reactor and the operating time of the protective chambers without impairing the protection of the reactor is possible on the basis of the discovery that the blockages in the protective chamber do not occur at a constant rate, but occur at times faster and at times more slowly. In spite of this, a substantially complete desalination of the insert can be achieved at any time in the thrust chambers if these are operated at a temperature that is just sufficient for desalination of the insert. The theoretical background to this behavior has not been fully elucidated; however, it is assumed that the optimum working temperature or optimum temperature range of the protective chamber. or several protective chambers between a minimum and a maximum, fluctuates. The minimum temperature leads to a deposition of the salts from the hydrocarbon feed, preferably to an essentially complete removal of the salts. Catalytically active materials are preferably used, da.als. Reactor poisons, effective heavy metal impurities by breaking up the carbon. ^{; 1} otallbincluni- "en rrindectens partially-

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removed. The protective chambers should be operated at the lowest temperature which allows partial conversion such as hydrodesulfurization of the insert, usually between 1 to 25 and preferably about 5 to about 20 % . Even at these low temperatures required for the deposition of the salts, the salt deposition always occurs in a matrix with carbon. If higher temperatures are used, that is to say at temperatures which are above that required for the deposition of the salts, no improvement in salt removal is achieved, but only an increase in carbon formation and thus faster clogging. The temperatures normally used at the end of the operating life of a reactor lead, for example, to very heavy carbon deposits and are therefore undesirable. Such high temperatures lead to the formation of carbon-containing precipitates and deposits, which lead to a significantly faster clogging of the protective chambers without improved removal of the salts.

When carrying out the method according to the invention, the protective chamber or chambers are used for desalination when starting up sufficient temperatures are used. In general, temperatures somewhat below or corresponding to the initial temperatures of the main reactor are satisfactory. The temperature in the protective chamber or chambers can to a certain extent

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be increased if the salt deposits with further Operations are to be improved; but this corresponds to. -not the increase in temperature in the main reactor. The temperature of a reactor or protective chamber is seldom constant, especially not when an active catalyst is used as the catalysts lead to endothermic or: exothermic · reactions. For example, when using Hydrodesulfurization catalyses the outflow temperature greater than the inflow temperature, whereby the outflow temperature of factors such as catalyst activity, catalyst bed length, Use temperature and extent of the hydrodesulfurization reaction depends. Hence the operating temperature a reactor or a protective hood, preferably as equivalents expressed isothermal temperature. Equivalents isothermal Temperatures (EIT) are known expressions in catalysis to define the temperature of a non-constant unit; she relate to the temperature at which an actually isothermal unit corresponds to a non-isothermal unit Activity would show. In general, the preferred hydrodesulfurization processes employed are EIT a use of coolant in the protective chamber is no longer possible than 1/3 to about 2/3 and preferably not more than 1/3 of the temperature difference between the initial and final temperature of a Throughput of the main reactor be above the initial temperature of the main reactor.

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In other places this means that the EIT is a protective. chamber must be kept during operation at a temperature not higher than the EIT temperature of the Main reactor at the start of operation plus 2/3 and preferably not more than 1/2 of the temperature difference between the start and end of operation of the main reactor.

The total amount of catalyst used in one or more protective chambers is generally less than 20 % and often less than 10 % of the weight of the catalyst used in the main reactor or reactors. About 5 to about 8% by weight of the amount of catalyst used in the main reactor are preferably used in the protective chamber or chambers. The height of the catalyst bed in the protective core depends on the throughput rate used and the surface mass rate. Depending on the salt content of the insert, a throughput rate (LHSV) of the insert through the protective chamber is generally sufficient

ν about 2 V / h / V to about 10 V / h / V and preferably from about 5 V / h / V to about 8 V / h / V completely off the main reactor to protect against clogging. In relation to the throughput rate, the minimum bed depth of the catalyst is in the Protection chamber directly with the surface mass velocity linked to the fluid through the protective chamber. The surface mass velocity a liquid through the protective

chamber is generally between about 227 kß / n / 0.0929 m

to about 2270 kg / h / O.929 m and preferably by about 907 to

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2 '

about 1360 kg / h / 0.0929 m of the protective chamber cross-section. When using the operating equipment usually used with mass velocities of about 907 to 130 kg / h / 0.0929 m ^2, a catalyst bed with a height of about 1.50 to 3.05 m in the protective chamber is completely sufficient to close the main reactor before clogging protection..

Preferably the operating conditions are the first. Protective chamber of a series, also in terms of size, optimized, so that this unit alone can hold back essentially all of the contaminating salts. In this embodiment the invention, the second protective chamber serves as an additional or alternative protective chamber to protect the "· Main reactor if the first protection chamber fails or if it is temporarily required for cleaning and reloading with the The catalytic converter is switched off the second protective chamber, except "when the first protective chamber is temporarily switched off from the series, as the upstream one Reactor.

When carrying out the method according to the invention, the integrate particularly favorably in hydrodesulfurization processes lets use it in one with a catalyst Filled protective chamber initiated, its EIT temperature is just sufficient to desalinate the insert; in general it is sufficient to continue at this temperature> that is, at a constant EIT temperature "throughout

2 0 9 8 A 2 / Ί 0 8 7 ^:

Operating to work even "when the temperature im Main reactor must be increased slowly ·. The feed flowing out of the first protective chamber becomes the inlet opening of the catalytic reaction zone of the main reactor where it comes into contact with the catalyst and depending on the type of catalyst, the other Reaction partner and the reaction conditions in the main reaction zone is converted. The reaction temperature in the main reaction zone, may initially be between about 149 ° C to 649 ° C, depending on the reaction to be carried out. In cracking and hydrocracking, the onset temperatures are generally about 316 to 538 C. In hydro refining processes such as hydrodesulfurization and hydrodenitrogenation, the temperatures are usually between about 260 to Hl »l ° C.

For example, if the temperature in the main reaction zone is kept at about 343 ° C at the start of the reaction with a freshly regenerated catalyst, the temperature is also kept at about 343 ° C in the protective chamber. The use is continuously fed into the protective chamber and then into the main reaction zone introduced; clogging due to Saiz deposits only occurs in the protective chamber while on the catalyst in the main reaction zone slowly precipitates and deposits only from carbonaceous and / or

Organonetallic compounds form, so that a total of a slowly increasing blockage in the protective

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chamber and a drop in catalytic activity in the main '· · train reactor. To the slow decline of the catalytic. 'To compensate for activity, the temperature in the main reactor slowly increased. When increasing the temperature by heating the insert before performing through the protective chamber would * would be made as the progress Operating time also in the Schutzkair.mer step by step increasing temperatures occur; then would the protective chamber much faster without an improvement and increase in Desalination speed of the insert become clogged

This adverse effect can be seen in the implementation of the bypass method according to the invention, that the increase the temperature in the main reaction zone by other methods is carried out that do not increase the initial operating temperatures. in the protective chamber. They are a © series. ' known of processes that can be used for this purpose

In a known method that can be used, for example between the reaction product from the main reaction zone and the effluent Use of a heat exchanger from the protective chamber, are interposed, so that the temperature of the outflowing feed from the protective chamber to the desired reactor inlet temperature can be increased. -.

Another known method is, for example, that the outflowing insert from the protective chamber with a

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separates heated reflux gas that is mixed thereby the temperature of the outflowing insert from the protective chamber to the desired inlet temperature for the Can increase main reaction zone * Another suitable method is that an inert gas or a reaction gas such as hydrogen, if hydrogen is required in the conversion process »is preheated beforehand and that this preheated gas with the outflowing insert from the protective chamber prior to introduction into the reaction zone is mixed. In any case, care should be taken to keep the temperature in the protective chamber as low as possible low, according to the initial temperatures, while the temperature in the main reaction zone is used to compensate of slowly occurring losses of the catalytic Activity is gradually increased. When performing the According to the process of the invention, the reaction conditions both in the protective canon and in the main reaction zone adjust to an optimum.

In general, those loaded with the impurities will be Catalysts from the Sehutzkairaaern not reused. If necessary, however, the inorganic metal salts can be removed from the material of the protective chambers according to known methods Methods and depending on the type of metallic impurities are carried out. For example, the protective chamber of the f) impurities that form droplets are cleaned by simply washing them out will; there is a much more effective method

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however _, that the material must first be treated with an oxygen-containing gas, such as air or a diluted oxygen stream, at moderately elevated temperatures too dispersible
Forms of metallic impurities such as sulfates, converted. After the oxidation, the solubilized impurities can be washed out with an aqueous solvent. To remove non-volatile soluble salts such as sodium chloride or sulfates, the aqueous solvent can only consist of water.
If less readily soluble impurities are present, the washing liquid should preferably be weakly alkaline. Instead of the oxidation treatment of the loaded material from the Sehutzkairimer, other known methods for removing carbon-containing compounds, such as steam treatment, can also be used before washing.

The following example is intended to explain the invention in more detail.

example

An insert made from Safaniya atmospheric residue oil was made together with "hydrogen through two protective chambers connected in series before hydrodesulfurization of the insert in one Main hydrodesulfurization reactor passed. The temperature of the Use when flowing into the protective casing is through-

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flow through a heat exchanger and the higher temperature required in the hydrodesulfurization reactor, especially in the further course of the operating time, is achieved by mixing a hot hydrogen gas stream with the cooler mixture of feed and hydrogen shortly before entering the hydrodesulfurization reactor. As a catalyst% silica and 3.5% by weight of molybdenum oxide is in the two protective chambers and in Hauptreaktor.ein Äluminiumoxydträger with content of 2.0 wt% cobalt oxide, and 12.5 weight used...; the surface of the catalyst

2 3

was 310 m / g, the pore volume was 0.50 cm / g. and

the surface had pores with a diameter of 30 to 80 % and 174 m ² / g. on.

The operating conditions of the two protective chambers and the Main reactor were as follows:

Protective chambers reactor EIT temperature in ⁰ C 371 Beginning 354 End of 4l6 ρ
Overpressure in kg / cm 56.2 56.2 Inlet gas in Nm ^ per 0.159 m ^ 84.93 84 ^ 3 Oj DD
7> iip 100 100 Throughput speed V / h / V 3 0.3

The composition of the introduced into the protective chambers Use and the final product obtained are in the following Table too

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mission End product API ° 11. 4 16 · Weight? S. 4.2 1-7 Ni in ppm '. - 26th 15th V in ppm 93 48 Na in ppm 82 0 Weight% Conradson-C 14th 9 ■

When operated under the specified conditions, the hydraulic, desulfurization reactor, (and the second connected Schutzkamnser) evenly and effectively without difficulty operated for about 12 months. The first protective chamber in the series, on the other hand, is already operational after about 3 months clogged (pressure drop in the protective chamber from 7> Q3 kg / cm overpressure) and must be switched off so that the Catalyst removed and fresh catalyst filled in ' can.

An analysis of the plugged catalyst from each of the two Protective chambers result in the following values;

% By weight - · Protective chamber ^ No. Schutzkammer_Nr ^ _2

i Na 15.3 15-5

Cl 8.6 3-9

Fe '2.5 ·' 2.4

Ni 2.3 2 .1-

Y- 9.4 10 .. 3

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Worm the same oil under appropriate conditions,

but without the use of protective chambers, was processed.

is the reactor after only two months of operation completely clogged.

The inventive method can be used for a variety of hydro refineries. Are particularly preferred carried out according to the invention hydrodesulfurization, their main operating conditions within the main reactor are as follows:.

overpressure in kg / cm ² 211-211 35.2 - 70.3

Temperature in ° C

Beginning 3 ^ 3 - 427. "357 -

End of ' h5 * i / "!''- 4-16

Throughput speed in V / h / V Q.l-10 1.5-2

H ₂ , purity in % by volume 50-90, 75-85

H ₂ throughput in Nm. ⁵ each 0.159m ³ , 1 ^ 15-28317, 2831-1 ^ 150

High-boiling inserts are preferred as feed materials used with a relatively high content of sulfur, asphaltenes, metals and ash. The stakes are in generally from liquid and solid hydrocarbons that are in the fluid state during the conversion reaction, i.e., in the form of liquid or vapor, while the end products of the conversion reaction are usually lower-boiling Connections are. A particularly frequent blockage of the reactor

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causative and therefore for the implementation of the invention A particularly suitable use for this process is a residue obtained from the atmospheric distillation of crude oil. oil. About 30 to 100 wt. # Of such inserts have one Boiling interval of above 4δ2 ° C. Such insert materials usually have the following typical properties:

Another Ber calibration narrower range% with boiling range above 482 ° C
Density ° API. .

Viscosity, Sys.® 50.0 ⁰ C wt. % S wt. JS.N Total metals in ppm Vanadium (ppm) Nickel (ppm) Sodium (ppm) wt. % Asphaltenes Pour point in C

Such feedstocks can be used in various ways Conversion into usable end products are dealt with. You can a hydrorefining such as hydrodesulfurization or hydrodenitrogenation to lower the sulfur or Nitrogen content or they can through

30-100 50 * -100 ~ 5 to 25 10-20 50-5000 + 100-1000 1-8 3-6 0-1 0.001-0.5 20-1000 . 80-500 10-500 3Ο-3ΟΟ 5-200 10-100 IO-I5O 20-80 1-40 2-20 -17.8 to 93.3 -3.9 to 37.8

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Hydrocracking converted to lower boiling petroleum products will. These conversion processes earth almost exclusively in the presence of potentially long-lived catalysts carried out, which are frequently operated and regenerated. The total content of metallic impurities In the stakes, if given as ^, it appears to be relatively low in relation to the total stake, but the cum. ulative effect of metal impurities becomes very great, when the catalyst is used and regenerated frequently, especially when the losses of catalyst material are low and the catalyst life is long. Beat the metallic contaminants on the feed settles on the catalyst used, all of which are called "metals" Impurities are referred to, either in the form of free metals or as relatively non-volatile metal compounds are present. Such metals can be water-soluble or water-insoluble, but they are mostly at least partially dispersible in the oil or,. soluble. To the water-insoluble Connections also include those that are elementary Nickel, iron, vanadium or copper or their oxides, "sulphides" or decompose other salts. On the other hand, non / volatile water-soluble salts, such as chlorides or sulfates, of alkali metals such as sodium and potassium or of alkaline earth metals such as magnesium or calcium.

The catalysts can be in various physical forms depending on the nature of the process in which the insert is used

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and exist in different chemical compositions.-For Catalysts based on silicon dioxide and aluminum trioxide are used in numerous reactions. To those containing silicon dioxide Crack catalysts also include the naturally occurring activated clays as well as synthetically produced Mixtures that have long been known as catalysts in the hydrogenation of hydrocarbons. Silica Containing Catalysts contain silicon dioxide and usually 1 or more promoters such as oxides or sulfides of a metal of group VI B such as molybdenum or tungsten, optionally with metals of group VIII, in particular. Oxides or sulphides of nickel or cobalt. Active catalysts are also activated by the incorporation of metals from group VI "B and / or of Group VIII in a support of aluminum trioxide or a mixture of silicon dioxide and aluminum trioxide. Together with a support made of silicon dioxide and / or aluminum trioxide, other oxides effective as promoters such as for example zirconium oxide or magnesium oxide can be used. The catalysts can be in the form of beads, tablets or extruded pellets each. according to the type of procedure to be carried out are present.

The bulk chambers can have the same or a different catalyst as used in the main reaction zone, optionally they can also be particulate inert Material with a large total surface such as bauxite,

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o6 -aluminium oxide, activated carbon or silica gels or the Catalyst support as used in the main reaction zone, but without reaction promoters deposited thereon, contain.

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Claims (18)

Claims Ll. Process for the catalytic! Converting metal contaminated hydrocarbon feedstocks in a main reaction zone maintained under conditions of hydrocarbon conversion temperature and pressure, characterized in that plugging of the main reaction zone by a) introducing the hydrocarbon feedstock •. in an upstream contact zone, whereby the. Insert material comprising a particulate material with one for the precipitation of the contaminating inorganic salts and lower, but not very much large amounts of carbonaceous compounds on the contact material at a suitable temperature is brought b) that the flowing out of the upstream contact zone liquid hydrocarbon feedstock in transferring the main reaction zone in which the effluent feedstock is under hydrocarbon conversion reaction conditions with a hydrocarbon conversion catalyst is brought into contact ^ c) that the supply of the hydrocarbon feed into the upstream contact zone and the transfer of the outflowing feedstock from the upstream 209 842/1087 Reaction zone in the main reaction zone is carried out continuously while the inorganic contaminating Metal salts gradually collect on the particulate material in the upstream contact zone and while the catalyst activity in the main reaction zone due to the formation of carbonaceous and / or organometallic deposits on the catalyst in the main reaction zone are reduced, d) and that the temperature in the main reaction zone to maintain the catalytic activity is gradually increased, while the reaction temperature in the upstream Contact zone is kept below the temperature required in the main reaction zone, after a certain period of time the upstream contact zone due to the formation of metal deposits on the particulate Material clogged and the formation of deposits of inorganic metal salts on the catalyst in the main reaction zone is kept low. 2. The method according to claim 1, characterized in that the temperature of the upstream contact zone at a temperature between the initial temperature of the main reaction zone plus 2/3 of the temperature difference between the beginning and the end of the operating temperatures is held in the main reaction zone. 209842/1087 3. The method according to claim. 2, characterized in that the temperature of the upstream contact zone is not more than the starting temperature of the main reaction zone plus half the temperature difference between the beginning and the end of the operating temperature of ^the main reaction zone. 4. The method according to claim 1 to 3, characterized in that; that · the temperature of the upstream KoiitalizQne essentially is kept constant .. 5 .. procedure-according to. Claims 1 to k ,. characterized in that, the temperature · of the main.reaction zone after; Beginning of the operation: the temperature of the upstream: KöntateZiQjj heating is increased, and that the temperature = of the egg material. a temperature sufficient for desalting in the areshaped contact zone and that the temperature of the feedstock is increased after it leaves the upstream contact zone and before it enters the main reaction zone 6. The method according to claim 1, characterized in that 'as Particulate solid in the upstream, contact zone a conversion catalyst is used. 7. The method according to claim 1 to 6, characterized in that as feedstock a petroleum residue sol from atmospheric distillations of crude petroleum, in which about 30 to 100 % 20984271007 have a boiling range of above 482 ° C and the relatively large kengen sulfur, asphaltene, Contains metals and ashes. 8 «Method according to claims 1 to 7» characterized in that, that a plurality of upstream contact zones before the Main reaction zone used w rd, with at least one of the upstream contact zones, related to the others, parallel is maintained. 9. Verährennach claim 1 to 7> characterized in that a plurality of upstream contact zones upstream of the main reaction zone is attached, these contact zones in Are connected in series. 10. The method according to claim 9, characterized in that the continuous supply of the hydrocarbon feedstock is carried out in the upstream contact zones until inorganic * Salts, a blockage has occurred that can be detected by a considerable pressure drop within the contact zones, and that the hydrocarbon feed is then diverted from a first to a second contact zone, while the desalinated downstream one Use is initiated into the main reaction zone. 20884271087 11. Verfaiiren according to claim 1 to 10, characterized in that that as a catalytic conversion process in the main reaction zone hydrocracking is carried out. 12. The method according to claim 1 to 10, characterized in that that a hydrodesulfurization is carried out as a catalytic conversion in the main reaction zone. 13. The method according to claim 12, characterized in that as Catalyst is an oxide or sulfide of a Group VI metal. B, Group VIII or mixtures thereof is used. I ¹ I. Process according to claim 13 *, characterized in that an aluminum oxide carrier with 5 to 25 wt. # Of a sulphide of tungsten and / or molybdenum and 1 to 15 wt. # Of a sulphide of nickel and / or cobalt is used as the catalyst. 15 · Verfaiiren according to claim 13 or I ¹ I, characterized in that the carrier is 1 to 6 wt.% Silica contains. 16. The method according to claim 1 to 15, characterized in that the temperature in the main reaction zone is initially about 149 to 649 ° C. . -. 17. Verfaiiren according to claim 15, characterized in that the Initial temperature in the main reaction zone about 343 to 427 ° C amounts to. 209842/1087 18. The method according to claim 1 to 17, characterized in that that the hydrocarbon feed is together with hydrogen is passed through the upstream contact zone and. that the use with a throughput speed of about 2 to about 10 V / h / V is passed through the upstream contact zone. 09842/10