JPS6038034A - Preparation of mixture of soluble catalytic metal salt containing at least vanadium and nickel - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to the field of petroleum refining, and more particularly to a process for the conversion of hydrocarbon oils containing metals, in particular vanadium and nickel, by hydrogenation.

PRIOR ART The feedstocks used in the process of the invention are any hydrocarbon oils having a high boiling point, e.g. above 350'C and containing metals, and e.g. atmospheric to vacuum distillation residues, shale oils or It is a liquid hydrocarbon fraction derived from pre-bitumen, asphalt parts, or coal liquefaction.

Petroleum and petroleum fractions are very complex mixtures. Among these, in addition to hydrocarbons, there are various compounds mainly containing sulfur, nitrogen, oxygen, and metals. The amount and type of these compounds will vary depending on the origin of the crude oil and fraction considered. Generally, these are impurities that are harmful to fine petroleum products due to contamination, corrosion, odor and/or stability. Among the many methods recommended for their removal, the most widely used is catalytic treatment in the presence of hydrogen.

However, these processes face several difficulties, mainly due to the presence of asphaltenes and metals, which lead to catalyst deactivation under poorly controlled conditions.

The metallic agents responsible for this inertness can be present in the form of oxides or sulfides. However, they are usually in the form of organometallic compounds such as porphyrins and their derivatives. The most commonly occurring metals are vanadium and nickel. The total content of these metals is usually 1
More than 0 ppm by weight, often 100-5ooO ppm by weight
It reaches levels as high as pm.

The asphaltenes are present in the form of a colloidal suspension, and the colloidal suspension may solidify or precipitate onto the catalyst composition under the conditions of hydrorefining. Therefore,
Fixed bed hydrotreating of these feeds does not give satisfactory results due to catalyst inactivation due to coke and metal deposition.

In the prior art, for example, U.S. Pat.
No. 3 proposed the use of finely ground catalytically active metal compounds as catalysts for hydrogenation conversion. These are metal compounds selected from the group ■, ■, ■ or the iron group and in colloidal suspension or solubilized in a solvent, and for example vanadium, molybdenum,
It is a compound of tungsten, nickel, cobalt and arsenic. Once introduced into the feed, these convert primarily to sulfides and, during the course of the hydrofining process, form a slurry containing the sulfidation catalyst, asphaltenes, coke and various metal impurities.

Because of the relatively large amount of catalyst required for this process and the relatively high cost of the catalyst, it has been proposed to recycle the catalyst slurry to reduce the consumption of fresh catalyst. Techniques for this include separating heavy hydrocarbons and catalyst slurry from the total products exiting the reaction zone.

This operation is carried out by any suitable method, such as distillation followed by separation of the slurry containing the catalyst. Before recycling the slurry, a portion of the slurry is removed as a catalyst purge and replaced with approximately the same amount of fresh catalyst compound.

Still, this recirculation has some disadvantages. There is also wear and tear on pumps, ingots in preheating furnaces and reactors, and sometimes blockage in conduits.

OBJECTS OF THE INVENTION The object of the invention is to ameliorate these disadvantages and thus to reduce the difficulties in processing heavy hydrocarbon feeds containing, for example, at least 10 ppm by weight of vanadium and nickel as a whole. That's true.

The process of the invention, which involves the hydrocatalytic treatment of a heavy charge of hydrocarbons containing the constituent metals of the invention (in particular vanadium and/or nickel), comprises at least two of the catalysts introduced into the reaction zone.
The catalyst slurry or catalyst solid precipitate, some of which originates from the hydroconversion in the liquid phase of the metal-containing hydrocarbon charge and in the presence of a dispersed catalyst, is extracted in the liquid phase with an organic complexing agent. This treatment is characterized in that the treatment is carried out in the presence of a free oxygen-containing gas.

In accordance with the preferred method of carrying out the invention, the extraction process comprises approximately 0
Hydrogenation of the liquid phase in the presence of air or in the presence of pure oxygen or oxygen diluted with an inert gas at a temperature between °C and a temperature equal to the reflux temperature of the liquid phase containing the complexing agent. It is carried out on the catalyst slurry or solid catalyst precipitate resulting from the conversion.

According to another method of implementing the invention, the extraction process is carried out by a gas containing free oxygen, for example by air.
About 50°C to 500°C, preferably about 100 to 350°C
may be carried out on the pretreated catalyst slurry or solid catalyst precipitate at a temperature of from 5 minutes to about 20 hours, preferably from about 1 hour to about 10 hours.

In this way a solution of a mixture of soluble salts of the catalytic metal is obtained.

Catalyst slurry refers to the solid phase formed during such hydroconversion processes. This phase is finely dispersed;
Most often colloidal.

It has become. However, it may also be separated at least partially from the oil by physical methods such as filtration, centrifugation or distillation of a distillable liquid substance. The method is thus applicable to slurries that have been separated from oil, or slurries that have only been thickened by being only partially separated from oil. It also applies to slurries cleaned with easily removable paraffinic hydrocarbons such as C3-C7 paraffins.

Solid precipitate refers to a solid phase containing primarily metals or precipitating compounds and coke. This occurs during the hydrocatalytic treatment of heavy hydrocarbon feeds (mainly containing vanadium and/or nickel, and in some cases other metals used as catalysts in the catalytic treatments described below). Processing of the slurry to remove from the slurry the proportion of asphaltenes that are not converted to aromatic hydrocarbons is obtained.

Complexing agent refers to a compound capable of dissolving one or more metals (vanadium, nickel) or compounds of said metals in a solvent.

In an advantageous embodiment, the process of the invention comprising the hydrogenation catalytic treatment of a hydrocarbon feed containing metals (in particular vanadium and/or nickel) is characterized in that:

First, a reactant containing suspended solid particles (catalyst slurry) is combined with a hydrocarbon fraction (5) at least partially removed from the suspended solid particles (catalyst slurry). )-enriched fraction (B) from the reactants; secondly, at least a portion of fraction ω) is treated with a complexing agent in the liquid phase in the presence of an oxygen-containing gas; thirdly, separating the resulting solution from the insoluble residue; and fourthly, separating the resulting solution from the insoluble residue.

At least a portion of the solution is sent back to the catalyst zone.

The separation of fraction (8) and fraction (B) may also be carried out by distillation, in which relatively light fractions are collected. The boiling fraction.The separation may also be carried out by other methods, such as filtration, overnight or centrifugation.Whatever method is used, the separation need not be so precise. No. In fact, part of the hydrocarbon (the unconverted part of the reaction product or feed) may be left in the solution of the metal compound obtained.

According to another embodiment, the treatment with the complexing agent is preceded by catalysis with an aromatic hydrocarbon or a mixture of aromatic hydrocarbons, such as Hensen, toluene or an aromatic fraction, such as LightLcyc o oil. A slurry extraction process may also be performed. This treatment has the advantage of dissolving asphaltenes adhering to the catalyst slurry. During subsequent treatment of the slurry with a complexing agent, only metals are extracted besides asphaltenes.

The slurry may also be treated with the aromatic hydrocarbon and the complexing agent all at once.

The method is particularly advantageous for processing feeds containing at least 10 ppm by weight of metals (vanadium and/or nickel). The more metal the feed contains, the greater the advantage.

The amount of active catalytic metal to be present in the catalytic reaction zone may typically be introduced from 50 to 5000 pm by weight (slurry). However, if some of the metals are introduced in a new form, then the present invention allows the metals of the vanadium and nickel groups to be extracted in the form of said substances by an organic complexing agent in the hydrocarbon charge to be hydrotreated. It is important that we aim to introduce an average of at least 10 pIl+.

The extraction treatment of the part (B) of the hydrogenation reaction product rich in suspended metal components and using a complexing agent is carried out at room temperature or at
℃ to the boiling point of the complexing agent or their solvent used.

According to a first method of operation, a dilute solution of the complexing agent dissolved in the hydrocarbon is used. The concentration used depends primarily on the metal compound content of the catalyst slurry to be extracted.

Therefore, the concentration of the solution of complexing agent in the hydrocarbon is, for example, 0
．． It may vary widely from 1% by weight to the solubility limit of the complexing agent in the hydrocarbon used as solvent. During the extraction process, the complexing agent is dissolved in the hydrocarbon oil along with particles of the metal compound. The oil phase may then be separated from the solid residue and returned to the feed to be treated. In fact, the oil phase of and contains the extracted metals in solution. The solid residue, consisting primarily of coke, may be discarded or used for other purposes.

The ζ1-kid forming agent may also be used in the form of a solution in alcohol or water. For extraction with aqueous solutions,
There is extraction of metals through the aqueous phase. The resulting solution can be directly recycled as a catalyst in hydrocarbon hydroconversion operations.

Metals may also be extracted from the catalyst slurry by pure complexing agents, ie, without dissolving these complexing agents in hydrocarbon solvents or water or alcohols.

The separation of the extraction phase and the solid residue after the addition of the complexing agent and the extraction may be carried out by any known method, for example by filtration or centrifugation.

Organic complexing agents for metals (particularly vanadium and nickel) may be selected from among a large number of compounds.

The gR forms are characterized by the presence in their molecules of one or more polar groups capable of reacting with precipitated metals of the catalyst slurry by forming salts or soluble metal complexes. Examples of such groups include ketones,
Mention may be made of carboxylic acid, aldehyde, ether oxide, alcohol and amine groups. What is listed here is not limited.

Examples of such compounds most preferred in the metal extraction method of the present invention include the following. Acetylacetone, benzoylacetone, oxalic acid, naphthenic acid, ethanol and dioxane.

It is known that such complexing agents readily react with metal oxides to form the corresponding salts or soluble complexes.

Surprisingly, as the examples of the invention show, in the presence of a gas containing free oxygen, the unroasted solid precipitate separated from the residual free asphaltenes or the unroasted catalyst slurry By reacting directly with complexing agents, it is possible to extract significant amounts of metals, especially vanadium and nickel, from the slurry and solid precipitate derived from the hydroconversion of heavy feeds of hydrocarbons. This was confirmed. These results are particularly surprising since gold F+Vft compounds do not react with such complexing agents.

In fact, this can probably be explained as follows. During the hydroprocessing of heavy hydrocarbon feeds, nickel and vanadium become thermodynamically stable s, vs4, V2s
5. In addition to stoichiometric sulfides of the V2s3 type, there are probably more than 10 possible mixtures of non-stoichiometric sulfides VSX (x with various values from 0.7 to 1.4). It precipitates in the form of a mixture of sulfides containing a significant proportion (GMELI).
NS HANDBUCH, Te1l B, Liefer
ungl, to, meV, pagas258-272
). It is believed that these non-stoichiometric metal sulfides are likely to form (metals exposed to oxygen can be extracted by complexing agents). For example, the reaction of acetylacetone with vanadyl sulfate is known.

vO804+2C5H802+Na2CO3→■0(C
5H70゜)2+Na2SO4"'l-H20+Co4
The vanadium- and/or nickel-containing extraction solution obtained in this way can be used as a catalyst in hydrotreating reactions of hydrocarbons in the liquid phase to remove undesirable constituents of these hydrocarbons, in particular sulfur compounds, nitrogen compounds and metal compounds. or to convert the heavy fraction of hydrocarbons into lighter fractions.

These operations are usually carried out in the presence of hydrogen at 300 to 500
℃ and a pressure of 1 to 30 MPa.

According to a first method of use of an organic or aqueous solution of the extract containing mainly soluble compounds of vanadium and/or nickel, as a hydrotreating catalyst for heavy hydrocarbon feeds, the desired concentration of vanadium and/or nickel is added. The calculated amount of this solution of the nickel compound is injected directly into the feed to be treated. This operation may be performed using a weighing pump.

According to another method of implementation, compounds of vanadium and nickel in the organic solution of the extract are added, for example trimethyl,
It may be reduced in advance with an organoaluminum reducing compound such as triisobutyl or triethylaluminum. Since these organoaluminum compounds are extremely susceptible to oxidation when exposed to oxygen in the air, it is necessary to remove the oxygen dissolved in the extraction solution before the reduction operation. This may be done, for example, by bubbling a stream of inert gas such as argon or nitrogen. For the same reason, the addition of organoaluminum reducing agents should also be carried out under an inert atmosphere. Atomic ratio A, 1! '／N
i 10V is generally 1 to 5 depending on the type of extraction solution.

In addition to vanadium and nickel originating from the feedstock, the extraction solution may also contain other metals, in particular metals that may have been introduced as addition catalysts or at the beginning of the reaction if appropriate. These metals are in particular molybdenum, tungsten, nickel, cobalt and/or iron.

Effects of the Invention Since the present invention is constructed as described above, it eliminates all the inconveniences such as wear and tear of pumps and blockage of preheating furnaces, reactors, and conduits that have occurred in the prior art, and therefore eliminates vanadium and nickel as a whole. At least So heavy ff1
Heavy hydrocarbon feedstocks containing pp+τ1 can be processed without difficulty.

EXAMPLES The extraction tests in Examples 1 to I3 below illustrate the extraction of precipitated metals, primarily vanadium and nickel, derived from the hydrotreatment of heavy hydrocarbon charges with various complexing agents.

Other examples are presented to illustrate the catalytic activity of the extraction solution obtained from the extraction reaction, containing primarily vanadium and nickel, when used as a catalyst in such hydroprocessing.

experimental method The characteristics of the three feeds used are summarized in Table I below.

Table 1 Characteristics of each feed used →=effect 30% by weight of gas mail or added C n
l) Iya Inn 8's Castle Distillation Residual Oil.

*3af an added with 35% by weight of light circulating oil
ya asphalt.

* 1 cS also "" 1 mj1'/sζn Preparation of insoluble solid precipitate and O catalyst slurry for extraction tests with forming agents Hydrotreating of heavy feeds of hydrocarbons is described below. The test is carried out under suitable operating conditions.

Each test shall be conducted in the following manner.

120 g of untreated heavy feed is introduced into the autoclave. At that time, the concentration calculated as elemental metal is 500
A catalyst of weight p p n+ is introduced. Purged with hydrogen and placed at room temperature under 100 bar. Heat at 380'C for 1 hour (pretreatment to aid in the formation of sulfided catalyst species) and maintain at 420°C for 1 hour (effective temperature of the reaction).

Cool and degas the autoclave. In this case, the solid precipitate or catalyst slurry insoluble in toluene is isolated according to the following method number. That is, a solid precipitate insoluble in toluene can be obtained by the following method. That is, after hydrotreating a heavy hydrocarbon charge, all of the product is recovered with toluene. This toluene solution was prepared under argon at 4 bar with a 0.2 micron “Millipore (Mi]
l1pore)j filter.

The solid material remaining on the filter is washed with toluene until the filtrate is colorless, and these solid precipitates are then subjected to drying by steam drying in the presence of air at 100° C. for two cycles.

The catalyst slurry is separated from the product after hydrotreating a heavy hydrocarbon charge by the following operating method. That is, the entire product recovered after hydrotreatment is precipitated with heptane.

The length of the heptane portion is reduced by an inclination σ1. Within this portion, maltenes (tM fats and oils) are soluble. After several precipitations with heptane until the heptane solution becomes almost colorless, the asphaltene portion is mainly unconverted,
The remaining product consisting of coke and precipitated metals is called the catalyst slurry.

The toluene-insoluble solid precipitates and catalyst slurries separated from the hydroprocessing products of various heavy charges of hydrocarbons are shown in Table 11.

Table ■ Water treatment of heavy hydrocarbon charge to obtain catalyst slurry and toluene-insoluble solid precipitate The characteristics of the slurry and the solid precipitate insoluble in toluene are shown in Table ■.

Table ■ Operating conditions for the extraction test of precipitated metals with a catalyst slurry and a toluene-insoluble complexing agent The apparatus used was a 100°
It consists of a spherical flask.

In a flask, add 1 g of toluene-insoluble precipitate or the amount indicated in Table 1 of the catalyst slurry to be treated, and 5 weights of 215 former in toluene or water or alcohol (high alcohol or "light cycle oil"). % solution 50
Enter 9. The reaction medium is heated at reflux in the presence of air for 3 hours. Then, the temperature is returned to about 50°C. after that,
The extract is separated from the remaining solid material by filtration over a 0.2 micron "Millipore" filter.

The extraction rate of extracted metals from toluene-insoluble precipitate is calculated by the following method.

The amount of extracted metal (x 100) e.g. toluene, water, 'light fist cycle - toluene-insoluble solid precipitate or catalyst slurry with solution of acetylacetone or organic acid such as oxalic acid or naphthenic acid in solution in oil or ethanol The extraction process is performed under the operating conditions previously described in the description of the experimental method.

The toluene-insoluble solid precipitate and catalyst slurry originate from the hydroprocessing of the hydrocarbon heavy feed (Table U).

Their characteristics are shown in Table ■.

In the case of young f, roasting was performed at 320° C. for 2 hours before extraction.

Toluene solution 14: The results of eight extraction examples of mainly nickel and vanadium from the precipitation are summarized in Table 3.

(Leaving space below) Table ■ Results of extraction of metals from toluene-insoluble solid precipitates This shows that the extraction rate can be obtained.

Tests 6 and 7 demonstrate that these other metals are recovered in the same manner and at comparable extraction rates when they are used in the form of soluble salts or metal complexes as starting catalysts. It shows.

Comparison of Tests 3 and 4 shows that, for example, pre-roasting the solid precipitate in air at 320°C for 2 hours before treatment with naphthenic acid is effective against pre-roasting the solid precipitate. This shows that the extraction rate is increased by about 20% relative to the precipitate.

This increase in the extraction rates of nickel and vanadium is probably due to the fact that the torrefaction allows the conversion of a small proportion of the sulfides in the precipitated nickel and vanadium sulfide mixture to oxides. Will.

Similarly, toluene or "light cycle oil"
Determination of the solution before or after the extraction treatment of the catalyst slurry derived from the hydrotreatment of hydrocarbon heavy feeds with a solution of 5% by weight acetylacetone in the solution shows that the recovery of nickel and vanadium can also be large. It shows.

Table V Extraction results of vanadium and nickel from catalyst slurry*
1*Metals derived from the dissolution of asphaltenes in the catalyst slurry 2*Balance table of metals extracted from the solid precipitate of the catalyst slurry As a catalyst for the hydroprocessing of hydrocarbon heavy feeds Examples of the use of vanadium and nickel extraction solutions The vanadium and nickel extraction solutions used as catalysts originate from extraction processes. Table I shows the results of this extraction process.
V and Table V.

Analytical Methods and Results Formula Asphaltene refers to the portion of the heavy product that precipitates upon addition of n-hebutane under the conditions of ffl rating NFT60115.

The asphaltene conversion is expressed and calculated in the following way.

AO = Asphaltene percentage of the initial charge.

A - Percentage of residual asphaltenes measured in the territorial waters or in the liquid phase of the sample taken after centrifugation.

Hydrodesulfurization is expressed in HDS%.

So - percentage of sulfur in the initial charge.

S - Percentage of sulfur remaining in the sample taken.

The metals (nickel and vanadium) are measured by atomic absorption and their removal is expressed in the same way.

Nio-N1 HDNi%--><100 Ni.

Rum content.

Ni, V - the content of nickel and vanadium in the liquid phase of the collected and territorial samples.

Example 1 This example describes the use of Cabi diluted with gas oil.
In the hydrotreatment test of the vacuum distillation residue of mas, this test shows the catalytic activity of the extract of the toluene-insoluble solid precipitate derived from the hydrotreatment of the same feed.

The extraction solution of nickel and vanadium was 6686 wt.ffi% vanadium and 0.32 wt.% nickel by a solution 507 of 5 wt.ffi% acetylacetone in toluene.
derived from the treatment of solid precipitate 17 [reference sample R10 (Tables ■ and ■)] containing . The extraction conditions were as follows: In a 100rnl spherical flask equipped with a water cooler, the atmosphere was
Reflux for 3 hours. After the reaction, the final solution is
The solids are separated by filtration through a 0.2 micron Millipore filter. Vanadium 5 by weight
6311 pm, 50 g of a solution containing nickel 24 PI)m are asked.

Cnl diluted with 30% gas fist oil by weight
] The vacuum distillation residue of imas (Table 1) is treated with hydrogen in the presence of a portion of the previous extraction solution in order to reduce the viscosity.

Experimentally, use the following method.

Vanadium and nickel extraction solutions 26V and Cf
67 Y and 30y of vacuum distillation residual oil of Cal]imas diluted with 30% gas/oil. After all of the toluene has been removed from this mixture by atmospheric distillation at 110° C., the entire mixture of charge and catalyst is introduced into the autoclave.

After purging the autoclave, hydrogen is introduced at 100 bar. The temperature rise is carried out in two stages.

To help form the so-called active sulfidation cycle before the reaction38
1 hour step at 0°C.

2 hour stage at 420°C.

Cool, degas, and recover all of the product. The division shows the following results.

568%, HDS=31% Example 2 (1: and Calculate 'I) The procedure of Example 1 is repeated except that the vanadium and nickel extraction catalyst solution is not included. The analysis of the product after the non-catalytic thermal reaction is as follows.

HDA=23%, HDV=l 9%, HD N 1-2
0%, HD S=7% Example 3 (comparative example) Instead of the extraction solution, a mixture of vanadium and nickel compounds prepared from vanadyl and nickel acetylacetonate, a chemical product of the company MERCK, is used. The test described in Example J is repeated, except that:

The preparation of this synthesis mixture was carried out in a manner that strictly adhered to the proportions of the extraction solution previously used in Example 1.

That is, acetylacetone 5 with a vanadium concentration of 563 wt ppm and a nickel concentration of 24 wt ppr11.
501 toluene solutions containing % heavy M were prepared.

CabimIts diluted with Gaskai Oil 30% by weight
To treat 3 og of vacuum distillation residue, a solution of 26.27 g of this synthetic mixture of vanadium and nickel was also added.
P was used first.

Analysis of the product after the reaction was as follows.

HDA=36.5%, HDV=81%, HD Ni
= 67%, HD S = 30.4% From these results, it can be seen that the tl
It has been confirmed that the vanadium and nickel extraction solution obtained can advantageously be reused as a catalyst (Example 1) and that the results obtained do not differ substantially from those obtained with fresh catalysts. I can do it.

Example 4 Example 1 is repeated, except that instead of the vanadium and nickel extraction solution obtained from the solid precipitate, an extraction solution obtained by extraction of the catalyst slurry with an acetylacetone solution is used as the catalyst.

The extraction solution used in the test in this example is extraction test n09.
(Table V).

The concentrations used are always the same. Zunaji, 500 ppm of vanadium calculated based on the raw material.

After the reaction, analysis of the product shows the following results.

HD A = 38%, HDV = 84%, HDNi =
70% HDS = 32% The results of this test show that the vanadium and nickel extraction catalyst solution containing asphaltenes was combined with the vanadium and nickel extraction catalyst solution by extraction of the solid precipitate from which the asphaltenes were removed. It shows that they are equally active.

The usefulness of the technique described in this example is clear. In fact, in the industrial implementation of such hydrotreating, vanadium and nickel can be recovered by direct extraction reaction of the slurry, purge or mixtures thereof, without the need to separate the solid precipitate from the remaining asphaltene fraction. It is possible to consider.

Example 5 The catalytic activity of the nickel and vanadium extraction solution obtained in extraction test 8 (see Table 1) and the same solution previously reduced with l-ethylaluminum is compared.

The same procedure as in Example 1 is carried out. However, the treated feedstock is not CBI)imas vacuum residue, but Boscan
of crude oil (Table 1).

Two hydrotreating trials were conducted.

First test Vanadium and nickel extraction solution previously reduced with triethylaluminum. Atomic ratio A
l/'v 1 N i is 3.

Run z Ij+h The same extraction solution of vanadium and nickel used as is as catalyst without reduction with ethylaluminum.

The analysis of the products of these two tests is summarized in the following table.

It can be seen from this table that pre-reducing the vapsium and nickel extracts before being used as hydroprocessing catalysts clearly improves the catalytic activity.

Example 6 Same as Example 1, in gas/oil! Interpreted Ca
Bimas vacuum distillation residual oil is hydrotreated. The only difference is that the extract is not an extraction solution with catalyst or acetylacetone, but an ethanol solution of 5 parts by weight of naphthenic acid (
Extraction test number 3) in Table IV. The ethanol of the extraction solution is completely removed by evaporation under reduced pressure at 1 hour at 1Q.degree. The remaining phase is a yellowish-brown liquid and is used as a catalyst.

The results of this test are as follows.

HD A, = 29th section, H, D V = 69%, H
D N i −=65%, HDS=30% Is the catalytic activity of the extract good overall?Example 1
Comparison with Acetylacetin confirms that the extraction of the same metal with acetylacetate is more active, especially in the conversion of asphaltenes (HDA in this case 38% versus 29%).

that's all 4 people outside 1st negative wire 1 [Phase] Inventor: Germain Marchi of

Claims (1)

Claims: (1) A method for preparing a mixture of soluble salts of catalytic metals containing at least vanadium and nickel, comprising: a) in the liquid phase of a hydrocarbon charge containing said metals and in the presence of a dispersed catalyst; The catalyst slurry or catalyst solid precipitate resulting from the hydrogenation conversion in the liquid phase is treated with an organic complexing agent in the presence of a free oxygen containing gas from about At a temperature between? n) and b) separating the resulting liquid phase containing the mixture of soluble metal salts. (2) A patent claim characterized in that a solid precipitate obtained by washing a catalyst slurry with an aromatic hydrocarbon is treated, said washing having the effect of extracting at least a portion of asphaltenes present in said slurry. The method described in item 1. 3. A method according to claim 1, characterized in that: (3) a catalyst slurry previously washed with at least one saturated hydrocarbon having 3 to 7 carbon atoms is treated; (4) Process according to claim 1, characterized in that a catalyst slurry is treated which is a 550"-cut of the hydrotreated product, and the 550"-cut is separated by distillation. . (Prior to the extraction treatment of the catalyst slurry or solid catalyst precipitate with the 51 organic complexing agent, the slurry or the solid catalyst precipitate is extracted with an oxygen-containing gas at a temperature of about 50 to 500° C. for a period of about 5 minutes to about 20 FrI. The method according to any one of claims 1 to 4, characterized in that the treatment is carried out. (6) The organic complexing agent is a β-diketone, a carboxylic acid, an alcohol or an ether oxide. (7) The method according to claim 6, characterized in that the complex forming agent is acetylacetone. (8) The catalyst slurry or the like contains at least one compound of a metal from the group of molybdenum, tungsten, iron, and cobalt.
The method described in any one of Section 5. (1) Any one of claims 1 to 8 wherein the mixture of soluble metal salts is obtained for use as a catalyst in a hydroconversion or hydrotreating reaction of a liquid-phase hydrocarbon feed. The method described in section. 00) The method of claim 9, wherein the feed comprises at least one undesirable compound of the group comprising sulfur compounds, nitrogen compounds and metal compounds. A mixture of all soluble gold S salts is added to the hydrocarbon charge of 1,000,000 M, calculated as vanadium metal and nickel metal.
The method according to claim 9 or 10, wherein the amount is used in a proportion of 50 to 5000 parts by weight. (I2) A mixture of soluble metal salts was obtained by treatment of a slurry or solid precipitate with acetylacetone,
A method according to any one of claims 9 to 11. (I3) Process according to any one of claims 9 to 11, wherein the mixture of soluble metal salts is obtained by extraction treatment of a slurry or solid precipitate with at least one carboxylic acid. (14) The method according to any one of claims 9 to 13, wherein the mixture of soluble salts obtained by the extraction treatment of the slurry or solid precipitate is reduced in advance with an organoaluminum reducing agent.