DE3423863A1 - Process and preparation of a mixture of soluble metal salts of principally vanadium and nickel, and the use thereof as a hydrotreating catalyst for heavy hydrocarbons in liquid phase - Google Patents

Abstract

A mixture of soluble catalytic metal salts of at least vanadium and nickel is prepared according to the invention by treating a catalytic slurry or a solid catalytic precipitate originating from a hydroconversion, carried out in a liquid phase in the presence of a finely divided catalyst, of a heavy hydrocarbon resin containing said metals, with an organic complexing agent in the liquid phase, and carrying out the treatment in the presence of a gas containing free oxygen at a temperature between about 0 DEG C and the boiling point of the liquid phase obtained from this treatment, and separating off the resultant liquid phase, which contains the mixture of the soluble metal salts. <??>At least part of this mixture is successfully used as a catalyst for the catalytic hydrogenation of a heavy hydrocarbon batch containing, as metals, at least vanadium and/or nickel.

Description

The present invention relates to the subject matter specified in the claims and leads to advantages in the field of petroleum refining in a hydrogenation conversion process of hydrocarbon oils, which contain metals, especially vanadium and nickel.

When carrying out the method according to the invention The hydrocarbon charge used can be any metal-containing hydrocarbon oil with a higher Boiling point, e.g. B. of over 350 ° C, act, for example to a distillation residue obtained at atmospheric pressure or under vacuum, to an oil from oil shale or bituminous sand to make an asphalt fraction or a liquid hydrocarbon fraction that consists of comes from coal liquefaction.

Petroleum and petroleum fractions are very complex mixtures, in which among the hydrocarbons there are various compounds, mainly sulfur, nitrogen, Contain oxygen and metals. These compounds may vary in amount and type each according to the origin of the crude oil and the fractions concerned.

These are usually impurities that are harmful to the good quality of petroleum products are related to pollution, corrosion, odor and / or stability. Among the numerous known methods the elimination of these compounds includes the catalvtic treatment methods in the presence of wet matter, which are the most common such methods.

With these treatment methods, however, difficulties arise, mainly due to the presence of Asphaltenes and metals are carried out under inadequate controlled process conditions lead to deactivation of the catalysts.

The metal compounds responsible for this deactivation can be present as oxides or sulfides; however, they are usually in the form of organometallic compounds Connections before, e.g. B. as porphyrins and their derivatives.

The most common metals are vanadium and nickel. The total content of these metals is usually at over 10 ppm (w / w) and, based on weight, often reaches values of up to 100 to 5000 ppm.

The asphaltenes are in the form of a colloidal suspension, which under the conditions of hydrating Can agglomerate refining and deposit on the catalyst mass. So the fixed bed HVRotreating results such batches do not give satisfactory results and the catalyst becomes due to the deposition of coke and metals deactivated.

There has already been the use of catalytically active metal compounds in finely divided form as hydroconversion catalysts (see e.g. U.S. Patent 3,165,463). These are connections of the Metals of groups IV, V, VI or the iron group des

Periodic table in the form of a colloidal suspension or dissolved in a solvent, for example to compounds of vanadium, molybdenum, tungsten, nickel, cobalt and iron. When they are introduced into the hydrocarbon charge they mainly convert to sulphides, and as the hydro refining treatment progresses A sludge forms which contains the sulfided catalyst, asphaltenes, coke and various metal impurities contains.

Because the amount of necessary to carry out the process Catalyst is quite considerable and the cost of the catalyst is relatively high, it has already been proposed to recycle the catalytic sludge in order to reduce the consumption of fresh catalyst. To this Technique involves removing the heavy hydrocarbons and catalyst sludge of the entire reaction- the product leaving the zone. This separation operation is carried out using any suitable method,

z. B. by distillation and subsequent separation of the sludge containing the catalyst; before recycling part of this sludge is drawn off as a drainage catalyst and replaced by a practically equivalent Amount of fresh catalyst compound replaced. However, this recycling has several disadvantages, z. B. the need to use pumps, the pollution of preheating ovens and reactors, sometimes even the clogging of pipes.

The object of the present invention is to eliminate the disadvantages indicated and the difficulties in Treatment of heavy hydrocarbon batches which, by weight, total e.g. B. at least 10 ppm Vanadium and nickel have to reduce.

In the process according to the invention, which is the catalytic treatment carried out with hydrogenation of a heavy hydrocarbon charge, the metals (essentially

WM r ■ *

_Q_

union vanadium and / or nickel) contains, there is at least part of that fed into the reaction zone Catalyst from the extraction product, which is obtained by extraction of a catalytic sludge or a solid catalytic precipitate resulting from the hydroconversion in the liquid phase of a containing the specified metals Hydrocarbon charge originate in the presence of a finely divided catalyst, with an organic one Complexing agent is obtained in the liquid phase, this extraction in the presence of a free oxygen containing gas takes place.

According to a preferred embodiment of the invention, the extraction treatment is carried out on a catalytic basis Sludge or a solid catalytic precipitate applied, resulting from the hydroconversion s-catmnen unct in the liquid phase at a temperature between about 0 C and one of the reflux temperatures of those containing the complexing agent liquid phase corresponding temperature in the presence of air or of oxygen or of diluted with inert gases Causes oxygen.

According to a further advantageous embodiment of the invention, the extraction treatment is carried out on a catalytic basis Sludge or a solid catalytic precipitate applied previously with a free oxygen containing gas, e.g. B. air, at a temperature between about 50 and 500 ° C, preferably between about 100 and 350 C for a period of time between 5 minutes and about 20 hours, preferably between about 1 hour and 10 hours, were treated.

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

The term catalytic sludge is to be understood as the solid phase that changes in the course of such a hydroconversion treatment forms. This phase is finely divided

and is mostly in the colloidal state. she however, it can, at least in part, be separated from the oil using physical methods, e.g. B. by decanting, Filtering, centrifuging or distilling off the liquid distillable products. The inventive The method is applied to the sludge, which is freed from the oil in the specified manner or simply enriched is by separating only part of the oil. The method can also be applied to a sludge that washed with an easily removable paraffinic hydrocarbon, e.g. B. with a paraffinic Hydrocarbon with 3 to 7 carbon atoms.

Solid precipitation is understood to mean the solid phase, which essentially contains precipitated metals or metal compounds and coke and which are obtained is made by treating the precipitated sludge with an aromatic hydrocarbon that is extracted from this sludge The proportion of asphaltenes eliminated in the course of the hydrogenating catalytic treatment of a severe Hydrocarbon charge, essentially vanadium and / or nickel and optionally others in this catalytic treatment contains metals that can be used as catalysts, have not undergone any conversion. 25th

Complexing agents are to be understood as meaning compounds which are capable of removing one or more precipitated Bringing metals or metal compounds (vanadium, nickel) into solution in a solvent medium.

According to a preferred embodiment, the process according to the invention is characterized by the hydrogenating catalytic treatment of a hydrocarbon charge containing metals (essentially vanadium and / or nickel) comprises, in that the reaction product, which contains solid particles present in suspension (catalytic sludge) is treated in such a way that a fraction (A) of hydrocarbons, the

-ιοί at least partially of these present in suspension Solid particles are freed, and a fraction (B), which are enriched in the solid particles present in suspension (catalytic sludge) are separated and that at least part of fraction (B) with a complexing agent in the liquid phase in the presence an oxygen-containing gas treated in such a way is that at least a part of the metals of this fraction, in particular vanadium and nickel, is dissolved that the obtained solution is separated from the insoluble residue and that at least part of this solution in the catalytic Zone is returned.

Fraction (A) can be separated from fraction (B) by distillation. This way they become relative light fractions obtained, e.g. B. the fractions boiling below 550 C, which represent the desired process product; there may be other methods of doing this Apply, z. B. a filtration, decantation or centrifugation. No matter which method is used finds it is not absolutely necessary that the separation be very high; so you can part of hydrocarbons (unconverted reaction products or fractions of the batch) in the solution of the obtained Leave metal connections.

According to a further advantageous embodiment, the treatment with a complexing agent can be an extraction treatment of the catalytic sludge with an aromatic

QQ see hydrocarbon or a mixture of aromatic hydrocarbons, e.g. B. benzene, toluene or an aromatic fraction (z. B. a light cyclizing oil) precede: This treatment has the advantage that the asphaltenes adhering to the catalytic sludge are dissolved; During the final treatment of the sludge with the complexing agent, only the metals are extracted to the exclusion of the asphaltenes.

The mud can also be used simultaneously with an aromatic Hydrocarbon and a complexing agent are treated.

The method according to the invention is particularly valuable for the treatment of hydrocarbon batches containing at least 10 ppm (w / w) metals (vanadium and / or nickel) exhibit. Its value is greater, the more metals there are in the hydrocarbon charge.

The amount of catalytically active metals that must be present in the catalytic reaction zone is on a weight basis, usually 50 to 5000 ppm. Some of these metals can be recycled in the form of Suspension (obtained from sludge) are introduced; however, it is important that some of the metals are in the form of fresh metals is fed, and according to the invention it is provided that an average of at least 10 ppm (G / G), based on the hydrocarbon charge to be subjected to the hydrotreating process, of metals of the group Vanadium and nickel in the form specified, obtained by extraction with an organic complexing agent Bring product.

The extraction that takes place with the complexing agent for the treatment of a metal element present in suspension Fraction (B) of the process product of the hydroconversion reaction can be rich at ambient temperatures and even at 0 ° C up to the boiling point of the

gO used complexing agents or their solvents take place.

According to an advantageous embodiment, solutions which 'with complexing agents, dissolved in a hydrocarbon, are diluted for use. The applied Concentrations depend mainly on the content of metal compounds of the catalytic to be extracted Mud off. The concentrations of solutions of the

Complexing agents in a hydrocarbon can therefore be very different and z. B. from 0.1 wt .-% to the solubility limit of these complexing agents in the hydrocarbons used as solvents. In the course of the extraction treatment, the complexing agent dissolves in the hydrocarbon oil, which is used as Accompanying substance of the metal compound particles is present. The oil phase is then separated from the solid residues and can be returned to the hydrocarbon feed to be treated.

This oil phase contains the metals present in solution, that have been extracted. The solid residues, which mainly consist of coke, can be discarded or used elsewhere.

A complexing agent in the form of a solution in alcohol or in water can also be used. In case of a Extraction with an aqueous solution is used to extract metals that go into the aqueous phase. the The solution obtained in this way can be used directly as a catalyst for a hydroconversation operation of hydrocarbons be recycled.

The metals of the catalytic sludge can also be extracted with pure complexing agents; H. without that these complexing agents are in a hydrocarbon solvent or be dissolved in water or in alcohol.

After adding the complexing agent and carried out Extraction can be the separation between the extract phase and the solid residue according to any conventional known Method, e.g. B. by decanting, filtering or centrifuging.

The organic complexing agent for metals (especially for vanadium and nickel) can be among numerous compounds to be selected.

t 4 *

-13-

It is characteristic of the complexing agents that they are in their molecule have one or more polar groups which are capable of reacting with those present in the catalytic sludge precipitated metals are capable of forming soluble salts or metal complexes. Typical such groups are e.g. B. ketone, carboxylic acid, aldehyde, ether oxide, alcohol and amine groups, this listing does not represent any limitation.

As examples of such compounds, those according to the invention for the extraction of metals are most preferred can be named: acetylacetone, benzoylacetone, oxalic acid, naphthenic acids, ethanol and dioxane.

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

Surprisingly, it was found that considerable amounts on metals, especially vanadium and nickel, from sludge and solid precipitation resulting from hydroconversion come from heavy hydrocarbon batches, are extractable when complexing agents in the presence of a free oxygen-containing gas directly with the uncalcined solid precipitates separated from the remaining asphaltenes or the uncalcined catalytic slurries, as shown in the examples below; such a thing The result is completely unexpected, since it is known that the metal sulfides do not react with such complexing agents.

The explanation for this finding is probably as follows: In the course of the hydrotreating treatment of heavy hydrocarbon batches, nickel and vanadium are precipitated in the form of sulphide mixtures, which in addition to thermodynamically stable stoichiometrically composed sulphides of the types VS, VS ₄ , V ₃ S ₅ and V ₃ S ₃ one undoubtedly

substantial portion of a mixture of possibly more than ten non-stoichiometric sulfides VS, where χ varies from 0.7 to 1.4 (see Gmelins Handbook, Part B, Delivery 1, Volume V, pages 268-272). These non-stoichiometric metal sulfides are likely easily oxidized to sulphates on contact with oxygen in the air, the metals of which can be extracted with the complexing agent are. So is z. B. the reaction of acetylacetone with vanadyl sulfate according to the following reaction scheme is known:

VOSO ₄ + 2 C ₅ HgO ₂ + Na ₂ CO ₃ - VO (C ₅ H ₇ O ₂ ) ₂ + Na ₂ SO ₄ + H ₂ O + CO ₂

The extract solutions obtained in this way, which contain vanadium and / or nickel, can be used as catalysts for the purpose of being used in the hydrotreating reactions of hydrocarbons in the liquid phase the elimination of the undesirable elements of these hydrocarbons, in particular the sulfur compounds, the nitrogen compounds and the metal compounds, or to convert the heavy hydrocarbon fractions into lighter ones Convert factions.

These operations are usually carried out in the presence of hydrogen at 300
30 MPa carried out.

Hydrogen at 300 to 500 ° C under a pressure of 1 to

According to a first embodiment of the use of the organic or aqueous extract solution, which mainly Has soluble vanadium and / or nickel compounds, as a catalyst for the hydrotreating of heavy Hydrocarbon batches is the calculated amount of this solution of vanadium and / or nickel compounds, which corresponds to the desired concentration, injected directly into the batch to be treated. This surgery can with the help of a metering pump or with the help of any other device commonly used for this type of operation take place, either continuously or discontinuously.

According to a further embodiment, the vanadium and nickel compounds of the organic extract solution beforehand with an organoaluminum reducing agent, such as. B. Trimethyl, triisobutyl or triethyaluminum, reduced will. Since these aluminum-organic compounds are easily oxidized on contact with the oxygen in the air the reduction operation must necessarily be preceded by the removal of oxygen dissolved in the extract solution; this can e.g. B. by blowing a stream of inert gas, ζ. B. by argon or nitrogen. From the The same reason must also be given to adding the organoaluminum reducing agent under an inert atmosphere take place. The atomic ratios Al / Ni + V are usually 1 to 5, depending on the origin of the extract solution. the Extract solutions can be other than vanadium and nickel from the hydrocarbon batch Have metals, especially those that may be used as additional catalysts or to initiate the Reaction were introduced. These metals are in particular molybdenum, tungsten, nickel and cobalt and / or iron.

The following examples are intended to explain the invention in more detail.
25th

Examples

The following extraction experiments 1 to 13 show the treatment for the extraction of precipitated metals, mainly vanadium and nickel derived from hydrotreating processes of heavy hydrocarbon batches, with various complexing agents.

The remaining examples explain the catalytic activity of extract solutions obtained by extraction reactions, which mainly contain vanadium and nickel

1 their use as catalysts in such hydrotreating processes.

Carrying out the experiment

The properties of three batches used as starting material are given in Table I below,

Tabel

Vacuum residue asphalt SAFA crude product Cabimas / GO 30 Z NYA / LCO 35 'i Boscan

(D (2)

Density (g / cm)

0.967 at 50 ° C 1.063 at 20 ° C 0.918 at 15 ° C

Viscosity (cSt) (3) 1530 at 50 C

Sulfur, wt%

2.3

7.8 at 100 ° C 710 at 80 ° C

5.28

5.2

Ni (ppm)

60

75

97

V (ppm)

47O

224

1200

Alphalten η C (% by weight) 10.7

19.1

11.0

30 (1) vacuum residue from Cabimas, mixed with 3O % by weight gas oil.

(2) Asphalt from Safanya, mixed with 35% by weight of light cycle oil

(3) 1 cSt = 1 mm ² / s

Production of solid precipitates insoluble in toluene and of catalytic sludges for the extraction experiments with complexing agents

The hydrotreating treatment of heavy hydrocarbon batches was carried out under the process conditions given below.

The procedure for each experiment was as follows: 120 g of the Heavy hydrocarbon charge to be treated was placed in an open autoclave. Then it became the catalyst was added in the concentration calculated as the elemental metal of 500 ppm, based on the weight. It was then flushed with hydrogen and the whole thing under a pressure of 100 bar at ambient temperature set. This was followed by heating to 380 ° C. for 1 hour (pretreatment to promote the formation of sulfided catalytically active compounds) and for 1 hour at 420 C (effective reaction temperature). The autoclave was then cooled and the gas evaporated. It then became a solid precipitate insoluble in toluene or a catalytic sludge isolated, depending on the process used.

The solid precipitates insoluble in toluene are obtained when the following procedure is followed: After the hydrotreating treatment of the heavy hydrocarbon charge, the entire process product is taken up in toluene. The toluene solution obtained is on a "Millipore" filter of 0.2 o under argon at a Filtered pressure of 4 bar. The solid products remaining on the filter are washed with toluene, until the filtrate is colorless. The solid precipitates obtained were then treated by dry foaming 100 ° C. for 2 h in the presence of air.

The catalytic sludges are derived from the hydrotreating heavy hydrocarbon batches

Process products separated as follows: The all products with heptane obtained after the hydrotreating treatment. The heptane fraction in which the Malthene (resins and oils) are soluble, is separated by decanting. After several precipitations with heptane, until the heptane solution is practically colorless, the remaining products, which are mainly composed of the not converted asphaltene fraction, consisting of coke and precipitated metals, called catalytic sludge.

The solid precipitates insoluble in toluene and the catalytic sludges resulting from the hydrotreating products Different batches of heavy hydrocarbons separated are shown in Table II below .

TABLE II

Hydrotrating experiment no.

used after Hydro-Charqe treating

separated products

Designation of the products used and the products removed

1 Cabimas / G.O Toluene insol
lich R 10 VO (ACAC) ₉ 2 Il π RIl ti 3 Il Il R 12 It 4th Il Il R 13 ft 5 Il more catalytic
mud R 20 tr 6th Safanya / LCO Il R 30 It 7th 11th Toluene insol
lich R 31 It 8th Il kataIyt i scher
mud R 40 VO (ACAC) ₂₊ Al (Et) ₃
(Al / V = 3) 9 Il Il R 50 VO (ACAC) _o + Nx (ACAC) 10
11
12th Raw product
Boscan
Il
Il Il
Toluene insol
lich R 60
R 70
R 80 (V / Ni = 2.6)
Il
Molybdenum naphtenate
Iron naphtenate
+ Al (Et) Al / Fe = 3 13th Il Il R 90 VO (ACAC) ₀

The properties of these catalytic slurries and solid precipitates insoluble in toluene are in the listed below in Table III.

Tabel

III

Designation amount of in amount of

of the samples toluene catalytically

insoluble appearance

Products (g) sludge (g)

Fluorescence value X sulfur

V Ni other% by weight% by weight by weight by weight

R 10 1.50 - 6.86 0.3 :: - 1.13. R 1 1 1.45 - 7.10 0.34 - 1.19 R 12 1.58 - 6.62 0.32 - 1.11 R 13
R 20
R 30 1.47 8.42
15.13 7.00
not
best.
M. 0.34
not
best.
I! - 1.18
not
best.
Ii R 31
R UO
R 30 1.51 11.69
13.75 5.30
not
best.
Il 0.18
not
best.
It - 2.86
not
best.
Il R ö0 - 8.05 Il Il - It R 70 1.60 - 10.59 0.50 3.75 (M ^ 2.41 R 30 1.57 - 11.16 0.53 3.82 (Fe) 2.55 R 90 1.59 11.02 0.51 2.55

Process conditions in the attempts to extract precipitated metals with the complexing agents

The device used consisted of a 100 ml flask, on which an open reflux condenser through which water flowed was mounted.

1 g of precipitate insoluble in toluene, or the amount shown in Table III, was added to the flask

catalytic sludge to be treated and 50 g of a 5% strength by weight solution of a complexing agent in toluene or in Water or in a light alcohol or in "light."

Cycle oil "introduced.
5

The reaction mixture was heated to reflux in the presence of air for 3 hours at which time the temperature rose about 50 C was brought. Thereafter, the extract solution was removed from the remaining solid products by filtration on a 0.2 micron "Millipore" filter.

The extraction amounts of the metals extracted from the precipitates insoluble in toluene were calculated as follows:
15th

" _Ί _, _. . , Amount of metal extracted (q) χ lOO

Extraction yield (%) =: r—- τ ~ ,, -:

Amount of xm precipitate present before the start of the reaction

Examples of treatment methods for the extraction of vanadium and nickel

The extraction treatments of the toluene-insoluble solid precipitates and the catalytic sludges with solutions of acetylacetone and organic acids, e.g. B. oxalic acid or a naphthenic acid dissolved in toluene in Water, in "light cycle oil" or in ethanol, were run under the process conditions as above were described in connection with the explanation of the experimental procedure.

The solid precipitates insoluble in toluene and the catalytic sludges came from previous hydrotreating processes of heavy hydrocarbons (see Table II). Their properties are listed in Table III.

In certain cases, calcination was ^{carried out at 320 °} C. for 2 h before the extraction.

The results of eight examples of metal extraction, mainly of nickel and vanadium, from insolubles in toluene Precipitations are listed in Table IV below.

10

Table IV

15th 20th 25th

Extraction attempt no.

Name calcination solution of the sample used at 320 C / 12 h

Complexing agent
(5% by weight)

Extraction

lot (%)

V Ni others

30th

1 R 10 no ACAC / toluene 41 38 I. - 2 R 1 1 Yes Oxalic acid /
water 78 73 I. - 3
4th R 12
R 13 no
Yes ^h -
Naphthenic acid /
Ethanol
ty
Naphthenic acid /
Ethanol 51
75 47
68 56Ob) 5 R 31 no ACAC / toluene 42 37 75 (Fe: 6th R 70 Yes ACAC / toluene 56 56 7th R 80 Yes ACAC / LCO * 58 53 8th R 90 no ACAC / LCO * 54 49

35

"Light cycle oil"

The results show that with the help of the erfindungsgeinäße Method extraction quantities of vanadium and nickel can be obtained, which are usually over 50%.

Experiments nos. 6 and 7 show that the same procedure and with comparable extraction yields Also other metals can be recovered when they start in the form of soluble salts or Metal complexes can be used as a catalyst.

Are z. B. Runs Nos. 3 and 4 compared with each other, so it is also apparent that a calcination pre-treatment with air at 320 ⁰ C for 2 h prior to treatment with naphthenic the extraction yield to about 20% increase in comparison for the treatment of a previously not calcined solid precipitate.

This increase in the extraction yield of nickel and vanadium is presumably due to the fact that the Calcination is the conversion of an additional portion of the sulphides of the sulphide mixture of precipitated nickel and vanadium allowed in oxides.

Likewise, the contents of the solutions before and after the extraction treatment of catalytic sludges show that originate from previously carried out hydrotreating treatments of heavy hydrocarbon batches, with 5% strength by weight Solutions of acetylacetone in toluene or "light cycle oil" that recover nickel and vanadium can also be considerable, as can be seen in Table V below.

Tabel

Experiment Designation Content of the solutions Extra- Vanadium Nickel

No. of the cata- before the after the tion- extra- extra-

lytic reaction reaction medium hiert hiert

Sludge (1) (2) (ppm) (ppm)

V Ni ppm ppm

V Ni ppm ppm

9 R 20 233 42 972 75 toluene 739 33 10 R 30 86 43 610 83 toluene 524 40 11th R 40 CTv 45 644 87 toluene 553 42 12th R 50 ' 88 44 623 217 toluene 535 173 13th R 60 496 60 2125 136 LCO * 1629 76

* "Light cycle oil"

(1) The metals originate from the solution of asphaltenes in the catalytic Mud.

(2) Balance from the metals of (1) + the metals extracted from the • solid precipitates of the catalytic sludge are.

Examples of the use of vanadium and nickel extract solutions as hydrotreating catalysts for heavy hydrocarbon batches

The extract solutions of vanadium and nickel, which served as catalysts, came from the extraction treatments, the results of which are given in Tables IV and V.

Analysis methods and information on results

- Asphaltenes are the fraction of heavy products that are produced when n-heptane is added under the conditions the test standard NF T6O115 fails.

The conversion of the asphaltenes is expressed and calculated as follows:

% HDA = ^Ao " ^A
^ O χ 100

Ao
Ao: percentage of asphaltene in the initial batch

A: Percentage of asphaltene remaining, determined in the liquid phase of the sample taken after Decantation or centrifugation.

- The hydrodesulphurisation is expressed in% HDS as follows:

So - ς

% HDS = ^{bO b} χ 100 I

So J

So: percentage of sulfur in the initial batch

S: percentage of sulfur remaining in the sample taken.

- The metals (nickel and vanadium) are determined by atomic absorption, and their elimination is as follows expressed:

¹ HDNi = ^Ni o " ^Ni _x

Ni
ο

% HDV = ο ^v

χ 100

V
ο

Ni, V: content of nickel and vanadium in the initial batch

Ni, V: content of nickel and vanadium in the liquid

Phase of the sample taken after it has been decanted.

example 1

This example shows the catalytic activity in an experiment with a vacuum residue obtained by hydrotreating from Cabimas, diluted with gas oil, and an extract of solid precipitate insoluble in toluene, which comes from a previously carried out hydrotreating process of the same batch.

The extract solution of nickel and vanadium is obtained by treating 1 g of solid precipitate, the 6.86 Contains wt .-% vanadium and 0.32 wt .-% nickel, sample designation R 10 (in Tables II and III), with 50 g a 5% by weight solution of acetylacetone in toluene. The extraction conditions were: reaction time 3 h under Reflux, under air, in a 100 ml flask fitted with was equipped with a reflux condenser through which cooling water flowed. After the reaction was carried out, the obtained Solution separated from solids by filtration on a 0.2 "Millipore" filter. It 50 g of solution containing 563 ppm vanadium and 24 ppm nickel, based on weight, were obtained.

It became a vacuum residue from Cabimas, which used to reduce its viscosity with 30% of its weight Gas oil was diluted (see Table I) with hydrogen in the presence of part of the extract solution described above treated.

The experimental implementation was as follows:

26.67 g of vanadium and nickel extract solution were mixed with 30 g of vacuum residue from Cabiraas, diluted with 30 % by weight of gas oil. After the toluene had been completely removed from this mixture by distillation at atmospheric pressure and 100 ° C., the total amount of mixture plus catalyst was introduced into an autoclave. After flushing the autoclave, hydrogen was introduced under 100 bar. The temperature was increased in two stages:

- First stage at 380 C for 1h to ensure the formation of to promote sulphided active compounds before the actual reaction,

- Second stage at 420 ° C for 2 hours.

It was then cooled, the gas evaporated and all of the product isolated. The analyzes carried out showed following results:

HDA = 38%, HDV = 79%, HDNi = 68%, HDS = 31%

Example 2 (comparative example)

The procedure described in Example 1 was repeated, with the exception that no catalytic Vanadium and nickel extract solution was used. The analysis results for process products according to non-catalytic thermal reaction were as follows:

HDA = 23%, HDV = 10%, HDNi = 20%, HDS = 7%

-28-Example 3 (comparative example)

The procedure described in Example 1 was repeated, with the exception that instead of the Extract solution a mixture of compounds of vanadium and nickel were used, that of vanadyl acetylacetonates and nickel and which were chemical products from MERCK.

The preparation of this synthetic mixture was carried out in such a way that the proportions of the im Example 1 above used extract solution were strictly adhered to, d. H. that 5o g of toluene solution with a Content of 5% wt .-% acetylacetone and the concentration of vanadium 563 ppm and the concentration of nickel were 24 ppm by weight.

For the treatment of 30 g vacuum residue from Cabimas, diluted with 30% by weight gas oil, again 26.6 7 g this solution of the synthetic mixture of vanadium and nickel is used.

The analysis results of the products obtained after the reaction were as follows:
25th

HDA = 36.5%, HDV = 81%, HDNi = 67%, HDS = 30.4%

Based on these results, it can be determined that the extract solution of vanadium and nickel, which by Extraction treatment of a solid precipitate from the previously performed hydrotreating treatment with a dilute solution of acetylacetone was obtained, advantageously reusable as a catalyst is (see. Example 1) and that their effect does not differ significantly from the effect that with a fresh catalyst is obtained.

example

The procedure described in Example 1 was repeated, with the exception that instead of the Vanadium and nickel extract solution obtained from solid precipitates as a catalyst, the extract solution was used by the extraction treatment of a catalytic sludge with a solution of acetylacetone was obtained.

The extract solution used to carry out this example came from extraction test No. 9 (cf. Table V).

The concentration used was always the same, i. H. it was 500 ppm vanadium calculated in relation to Batch.

After the reaction had been carried out, the analysis of the products obtained gave the following results:

HDA = 38%, HDV = 84%, HDNi = 70%, HDS = 32%.

The results obtained show that the catalytic extract solution of vanadium and nickel, the asphaltene contains, is just as active as that obtained by extraction of solid precipitates that are free from Asphaltenes are preserved.

The importance of the process engineering described in this example is obvious and so can actually be used in industrial practice of such hydrotreating processes be proceeded so that vanadium and nickel by direct extraction reaction of the sludge, the Processes or mixtures thereof can be recovered and used without being forced to use the to separate solid precipitates from the remaining asphaltene fraction.

example

In this example the catalytic activity of the Extract solution of nickel and vanadium, which was obtained according to extraction test no. 8 (see. Table IV) and the same solution that was previously reduced with triethylaluminum.

The procedure was as in Example 1, except that the treated batch was not a vacuum residue from Cabimas, but a raw product Boscan (see Table I).

Two hydrotreating attempts were carried out. 15th

First attempt: extract solution of vanadium and nickel, which had previously been reduced with triethylaluminum. The Al / V + Ni atomic ratio was 3.

Second attempt: The same extract solution of vanadium and nickel that was used as a catalyst, without Reduction with triethylaluminum.

The analysis results of the process products of these two experiments are listed in the following table.

Hydrotreating catalyst results

Attempt no.

1 extract of V 45 84 79 37 and Ni, reduced with

Al (Et) ₃

2 Extract of V 32 76 69 31 and Ni, not reduced with

Al (Et) _n

The results obtained show that the previous reduction of the extract of vanadium and nickel, before its use as a hydrotreating catalyst brings about a clear improvement in the catalytic activity .

example

^:

A vacuum residue from Cabimas diluted with gas oil, was subjected to a hydrotreating treatment as in Example 1. The only difference was that The catalyst used is not an extract solution with acetylacetone, but an extract with an ethanolic solution of 5 wt .-% naphthenic acid (extraction test No. 3 of Table IV). That Ethanol of the extract solution was completely removed by evaporation under vacuum at 100 ° C. for 1 hour. the the remaining phase was a brownish-yellowish liquid which was used as a catalyst.

The results of this experiment were as follows: HDA = 29%, HDV = 69%, HDNi = 65%, HDS = 30%

Although the catalytic activity of the extract of vanadium and nickel with naphthenic acid is overall good, it can When compared with Example 1 it can be found that the extract of the same metals with acetylacetone is more active, especially as regards the conversion of asphaltenes (38% HDA instead of 29% in the present Trap) concerns.

Claims (14)

Patent Attorneys European Patent Attorneys Dr. W. Müller-Bore * Dietrich Lewald DipL-Ing. 3 ^ 23863 Dr. Paul Deufel DipL-Chem., Dipl.-Wirtsdi.-Ing. Dr. Alfred Schön Or. Müller-Bor * and Partner · POB 260247 ■ D-BDOO Munich 26 _,, _, Uipl.-L.nem. Werner Hertel Dipl.-Phys. Dr.-Ing. Dieter Otto DipL-Ing. Ape. : 2266 Rd / nc ^- I 1856 INSTITUT FRANCAIS DU PETROLE
4, avenue de Bois-Preau
F-92506 RUEIL-MALMAISON Process for the preparation of a mixture of
soluble metal salts of
mainly vanadium and nickel, and
Use of the same as a hydrotreating catalyst for heavy hydrocarbons
in liquid phase Claims Process for the preparation of a mixture of soluble salts of catalytic metals which comprise at least vanadium and nickel, characterized in that one
5 a) a catalytic sludge or solid cataly- tables precipitate, which consists of a liquid phase in the presence of a finely divided catalyst carried out hydroconversion of a heavy hydrocarbon charge containing the specified metals. originate with an organic D-8000 Munich 2 FOB 26 02 47 Cable: Telephone Telecopier Infotec 6400 B Telex "* · ^F ~" «~~~ *. *" J net II ... 1 - «-«. / ion / no ί α ηα ψψ «-» TT t TTT in Qn * OO QA Al Κ-9Λ 9RC Kanplexiermittel i ⁿ liquid phase treated and the treatment is carried out in the presence of a free oxygen-containing gas at a temperature between about 0 ⁰ C and the boiling temperature of the products of that treatment liquid phase, and b) the liquid phase obtained, which contains the mixture of soluble metal salts, is separated off. 2. The method according to claim 1, characterized in that that treating a solid precipitate obtained by washing a catalytic sludge with the aid of a aromatic hydrocarbon that is responsible for the extraction of at least part of that present in the sludge Asphaltene causes is gained. 3. The method according to claim 1, characterized in that treating a catalytic sludge which was previously washed with at least one saturated hydrocarbon having 3 to 7 carbon atoms. 4. The method according to claim 1, characterized in that treating a catalytic sludge which represents a fraction 550 of hydrotreating products, of which fraction 550 is separated by distillation. 5. The method according to any one of claims 1 to 4, characterized q ₀ , that before the extraction treatment of the catalytic sludge or a solid katalvtischen precipitate with the help of an organic Komolexiermittel the sludge or precipitate with an oxygen-containing gas at a temperature between about 50 and 500 ° C for a <between about 5 min and 20 h. _oc between about 50 and 500 ° C for a period of time 6. The method according to any one of claims 1 to 5, characterized in that the organic complexing agent a ß-diketone, a carboxylic acid, an alcohol or an ether oxide is used. 7. The method according to claim 6, characterized in that
that acetylacetone is used as a complexing agent. 8. The method according to any one of claims 1 to 5, characterized in that there is a catalytic sludge uses, which inter alia. at least one compound of a metal from the group consisting of molybdenum, tungsten, iron and Having cobalt. 9. Use of a mixture of soluble metal salts obtained by the process according to Claims 1 to 8 is, as a catalyst for a hydroconversion or hydrotreating reaction of a hydrocarbon feed in liquid phase. 10. Use according to claim 9, wherein the hydrocarbon charge has at least one undesirable compound from the group consisting of sulfur compounds, nitrogen compounds and metal compounds. 11. Use according to claims 9 or 10, wherein the mixture of soluble metal salts is used in an amount which, calculated as vanadium metal plus nickel metal, is 50 to 5000 ppm (w / w) of the hydrocarbon charge matters. 12. Use according to any one of claims 9 to 11, wherein the mixture of soluble metal salts by treating a sludge or solid precipitate with the help is obtained from acetylacetone. 13. Use according to one of Claims 9 to 11, whereby the mixture of soluble metal salts by extraction treatment of a sludge or solid precipitate is obtained with the help of at least one carboxylic acid. 14. Use according to one of Claims 9 to 3, wherein the mixture of soluble solids obtained by the extraction treatment of a sludge or solid precipitate Q Metal salts are reduced with an organoaluminum reducing agent before they are used.