JPS596283A - Heavy oil two stage hydrogenation - 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 Background of the Invention The present invention is directed to the hydrogenation treatment (bydrop
rocessing) and 2C for further details.

This invention relates to the hydrogenation of oils containing significant amounts of components with boiling points below 500°C.

Recirculation of hydrogenated fractionffl? A number of methods for hydrogenating heavy oils have been proposed, including: US patent number! 1,147,2
No. 06 fj, 9m-quality oil feed (hba'/yoilf
eed ) Kaoru, ψ, in one step ゛C hydrogen donor solvent (
byclroHen-donor 5orbent)
and in a second stage hydrocracking the gas oil (Faε-011) fraction of the first stage product. U.S. Special W1 No. 6.238.118,
The gas oil fraction separated from the crude oil feed is hydrocracked and its hydrocrackate bottoms (hydrocracl+at
e bottoms) residual oil portion (residual
(fraction) as a hydrogen donor for thermal conversion.

Pasting
) discloses a method of hot soaking in a solvent. Part of the residual product? Circulate books. U.S. Patent No. 4.083,76
A two-stage 1 & δ coal conversion method is disclosed in which the oil containing the solid notch is extracted from a Shimano dissolver and then stirred in a ladle. British Patent No. 1,551,177 discloses a two-stage coal liquefaction process in which the product oil containing 1.5% is ladle-circulated from a second PP11 stage.

US Pat. No. 3,839,187 discloses a process for treating heavy oil using recycled hydrogen donor gas oil fractions and particulate solids. US time π1 4.090,
No. 917 is a hydrogen donor dilution.

premium coop; -(premium coksr
) 7% water using gas oil (ii,' 4-body diluent 1-7 method
ent cra, cking processSs)Y disclosed. United States Moe ("No. 4,111,787" is
Please disclose the conversion of coal/oil mixtures using oil-soluble catalysts.

US Times No. 6,186,180 1st No. 5.412
,010 and No. 4,116,819 G1-9 disclose a one-step method utilizing a Toms recirculation bar;
and.

U.S./V:f-edifuku')-635-814, all? J1
whole boiiiing product
t) σ) Discloses a one-step coal liquefaction method using recirculation L
2.4) In the present invention, quality oil is hydrotreated in a two-stage system, and the residual component, that is, the component with a boiling point σ above 500°C, is recycled from the second stage product to the first stage. let Some of this 500'C+ component is hydrotreated in its second stage, and the presence of recycled residual components in the first stage facilitates the transfer of hydrogen to the new feed component. It is believed.

Furthermore, recycling of residual components provides further opportunity for their conversion to lower boiling components.

More specifically, the present invention is a method for hydrotreating a heavy hydrocarbon oil containing a liquid component with a boiling point higher than 500°C.

(8) contacting the hydrocarbon oil with hydrogen under hydrogenation conditions in a first reaction zone to produce a first effluent having liquid components boiling above 500'C;

tb at least a portion of the first effluent portion containing liquid components with a boiling point higher than 1500° C. and hydrogen.

contacting under hydrotreating conditions in the presence of a hydrogenation catalyst to produce a second effluent comprising a liquid component boiling above 500°C; and

(cl) characterized in that at least a portion of said second effluent, said portion containing a substantial amount of liquid components boiling above 500° C., is recycled to said first reaction zone. [Liquid component with boiling point higher than 500°C] (11quid, component boil
ing above 500'C) is molten at the temperature and pressure of the system. or in a liquid state. Also included are hydrocarbon components including non-distillable components that do not boil below 500'C at atmospheric pressure and decompose in vacuum distillation before reaching their boiling point. This heavy oil is stored in a porous metal blister (
get, ter) particle 9 dispersed hydrogenation catalyst and/or
The pellets may also contain added solids such as coal or coal-containing particles.

DETAILED DESCRIPTION Heavy oil feedstocks suitable for the process of the present invention include crude oil, petroleum residues such as atmospheric and vacuum residues, reduced crud, deasphalted residues, etc. Oil, bituminous coal,” 1. Bituminous coal, brown coal and 111. Heavy hydrocarbon oils derived from coal including charcoal, as well as oil shale and tar sands.
rsand), gilson it
hydrocarbon liquids derived from e.g.

Typically, the hydrocarbon liquid feed is heated to 500°C.
Higher liquid components: about 10% by weight or more or about 20% by weight
! A: It will contain more than Lgb.

The process of the present invention provides at least 50% of crude oil, which is typical of petroleum residues and shale oil or shale oil fractions.
ppmw of total Ni+V or 50 ppmw of total Ni+V or more is particularly useful for hydrotreating heavy oil feeds containing more than Ni+V of soluble metal compounds. - Figure 1 shows the process when the feed contains no solids 2 or only small amounts of solids. Referring to FIG. 1, a zero heavy oil feed is added to line 5, mixed with hydrogen added through line 15 and recirculated oil (described later herein), and a first hydrogen Hydrogenation is carried out in the hydrogenation treatment zone 20.

If desired, an entrained catalyst
ly+t ) and/or contact particles (contact
particles) can be added through line 10. The first general hydrotreating conditions suitable for use in the present invention are as follows.

Hydrogen partial pressure higher than 65 atm, 350-500°C.

Preferably, the hot water temperature is within the range of 400 to 455°C, about 40°C.
a pressure of ~680 atmospheres, preferably 100-340 atmospheres,
and 655-655067e feed oil.

Preferably, the hydrogen gas flow rate of the supplied oil is 680 to 178 c3e/l, and the residence time is preferably 0.01 hour or more, preferably 0-1 to 10 hours, and more preferably 0.1 to 1 hour. The first stage is the hydrotreating zone.

Although preferably operated in the absence of carbon monoxide, small amounts of carbon monoxide may be present, eg, in the gas recycled internally to the hydroprocessing zone. If desired, this first stage hydrotreating zone can be plug flowed.
-flow) conditions, but in the first stage there is a turbulent fl
ow) conditions can also be used. Preferably, the feed flows upwardly through the first stage hydrotreating zone. The preferred feed-distribution scheme is:

Filed on June 19, 1980, entitled ``Gas Pocket Distributor for Upflow Reactors'',
It is described in US Pat.

If desired, the catalyst can be added through a finely divided catalyst cell line 10 as described below in the present specification). Or again,
First stage hydrotreating zone? It is also possible to operate in the absence of externally supplied catalyst-spanning contact particles.

All or part of the product of the first stage reactor and line 25
Pass through the contact reactor 30 in two passes.

The feed to the catalytic reactor 30 includes at least a portion of the first stage product boiling above 500°C and preferably all of the first stage product boiling at 200°C+. contains. If desired.

Light gases and lower boiling hydrocarbon fractions, such as C5-C8 naphtha fractions or lighter fractions, can be removed before the remaining first stage product enters contacting stage 30.

The catalytic reaction zone 30 is the second hydrotreating zone)]
So, fluidized bed - packed bed or fixed bed catalyst? contains. Preferably, all liquid feed to the second stage passes over the packed catalyst bed. Flow distributors, such as those described in the aforementioned US patent application Ser. No. 160,793, may also be used if desired. The packed bed can be moved periodically to replace the catalyst if desired.

The preferred catalyst for the second stage is Chemical Rubber Co.
Chemical' Rubber Co, ) (1
964) Handbook of Chemistry and Physics
ry and Physics) ] The hydrogenated component preferably contains at least a part of the hydrogenated component selected from Group VIB and Group 1 of the Periodic Table of the Elements, 45th Edition.

Can exist as a metal, oxide or sulfide. This hydrogenation component is 1, for example, alumina, silica and alumina.
It is supported on a flammable inorganic substrate such as silica, alumina-boria, silica-alumina-magnesia or silica-alumina-titania composites. Phosphorus promoters can also be present in the catalyst. Suitable catalysts include gamma-alumina supported 1 e.g.
MO of C001 to 20 of 0 and 0.5 to 5% of P
%' such catalysts were prepared based on the teachings of U.S. Pat. The second hydrogenation zone 30 is operated at a lower temperature than the first hydrogenation zone 20, generally from 615 to 455'C, preferably from 40 to 425'C, more preferably from 660 to 400'C.
°C, generally 40 to 340 atm, preferably 70 to 210
atmospheric pressure, and more preferably 140-190 atmospheres, generally 0.1-2. Preferably &to, 2 to 1.5. and more preferably operating at a space velocity of 0.25 to 1/h, generally at a hydrogen feed rate of 170 to 5j/l feed, and preferably 340 to 270,013/l feed, and even more preferably 550 to 7001j/l. .

The product from the second stage 30 exits through line 35 and enters a high pressure separator 40 where the gaseous portion is removed following line 50, including light hydrocarbon gases, sulfur oxides, carbon oxides and After removing the water, it is recycled. Light liquid products are removed from the high pressure separator through line 45 and relatively heavy liquid products g (min) are removed through line 55fX-.

At least a portion of the heavy liquid product exiting the catalytic reactor 30 is recycled to the first hydrogenation zone 20 through line 90. If desired, a lighter liquid, e.g. The P) circulation portion contains a liquid component with a boiling point higher than 500'G. [Substantial amount (su
bstandialamount) is the amount of time in the distillation column that is greater than the carryover of heavy fractions to the distillate fraction in the fractionator. This paleocycle portion should contain at least 5'1 of substances with a boiling point higher than 500°C;
And in general.

It will contain more than 10 kg or more than 20 gw of '+vJ' with a boiling point below 500°C. The final liquid product passes through line 60 to a fraction of 1
onater) 85, where it is rectified into product fractions 86, 87, 88 and 89). If desired, all or part of the relatively heavy fractions are passed to line 9.
Circulate F'I through 0.

Circulate with a ladle and measure 2+ 5006C 1. Generally the]: about 5 to 1 per 100 kg of heavy oil feed to the culm.
000kl? , more preferably in the range of 10 to 100 k17 per 100 kg of feed.
Embodiment 2 of the present invention is shown.

In FIGS. 2 and 6, elements correspond to the same numbers as in FIG. 1 and are operated in the same manner as in FIG. The solids may be 1 coal, oil shale fines, coal treated with various catalysts as described in U.S. Pat. bottom a
sh pa, rticle=+), coal liquefaction residues may be of a wide variety of materials, such as others of 7c'. The solid-body contact particles are preferably porous.

j f (i.e., non-vitreous, such as coal, alumina, silica gel, clay, etc., and added to the solid to impart catalytic activity) or a catalytic transfer metal; Transferable metallization 6. Does not damage the material at all or substantially. Spent catalyst fines that incidentally contain catalyst metal paulownia as a result of previous use may be advantageously used if economically viable.

The contact particles may have added T-catalyst controlling components.

The contact particles are preferably added through line 12 and suspended in the heavy oil feed, but if desired the particles are added through line 12 and suspended in the heavy oil feed, but if desired, the particles are
You can even make it exist inside. The particles are suspended in the feed to the first stage in the hydroprocessing zone 2.
Oil IQQl in 0<0.5-200 ky per g 1.
! Enough lt should be added to make up the rl form.

The contact particles are placed in a contact stage (Ca'talyticsta).
ge) 30'! It will pass through the pump 55 and exit with the liquid portion of the contacting stage product.

Solids can be separated from the final product in line 55 either before or after the old circulation oil. If desired 1 for example 2 rl O
Is it a light liquid like ni-, a relatively heavy part? zone 2
It can also be separated from the liquid in line 55 before being recycled to zero. As shown in FIG. 2, a portion of the liquid product from line 55 is transferred to one, for example, a conventional set sea. A solids separation zone 10 such as a filter, hydroclone or centrifuge is suitable, where a solids-rich portion 15 and a solids-poor portion 80 are separated. The remainder of the liquid from line 55 is recycled to first stage hydroprocessing zone 20 via line 90. If desired.

It is also possible to separate all or a portion of the solids from the solids-rich stream 75 and recycle them to line 9o as shown in point Y, fIA 77.

The function of the contact particles in this process is as a deposition site for coke and for metals such as nickel and vanadium present in contaminated feedstocks.
getter). Recirculating the contact particles accumulates enough metal that they can be economically recovered by conventional methods.

In addition to the porous contact particles, a finely divided hydrogenation catalyst could also be added to the first stage, for example through line 10. This dispersed catalyst contains translocated metal sulfides,
They can be added as finely divided metal compounds such as nitrates and acetates. Suitable transition metal compounds include:

Ni(NO3)2”6H20, NiCO3, (NH4)
6MO7024”4H20.

(NH4)2Mo04, Co(NO3)2'6H
20, CoCO3 and iron.

Contains the divine oxides and sulfides of cobalt and nickel. Alternatively, finely divided t: s
It can also be added as an aqueous solution of one or more water-soluble transition metal compounds, such as ammonium or alkali metal molybdates, tungstates or vanadates. Suitable emulsion catalysts and methods for their use are described in 1979, 1
U.S. Pat. No. 4,1 entitled Emulsion Catalyst for Hydrogenation Catalysts, issued to Moil et al.
Since it is described in No. 72,814, please refer to this specification 4. Alternatively, one or more dispersed hydrogenation catalysts may be used, such as molybdenum naphthanate, cobalt naphthanate, etc.
Oil-soluble compounds of organometallic compounds known in the art such as molybdenum oleate and others may also be added. If a finely divided iron compound is to be used, it must be brought into contact with sufficient H2S in order to convert the iron compound into a catalytic compound. The catalyst will pass through the first and second hydroprocessing zones and a portion thereof will be recycled with the recycle oil stream in line 90.

The concentration of the dispersed hydrogenation catalyst is preferably less than 20% by weight of the feed, and more preferably from 0.001 to 5% by weight of the first stage feed. be. When added as a finely divided emulsion, the emulsion should contain about 0.00005 to 0.005 kl of catalyst per kg of feed. This emulsion is preferably mixed with the feed by rapid agitation before entering the first hydrogenation zone where contact with any porous contact particles that may be used takes place. Furthermore, this fine, N1
The hydrogenation catalyst can be added to the first hydroprocessing zone along with the recycle stream. When added, the hydrogenation catalyst is preferably added at a rate sufficient to suppress coke formation in the first stage hydroprocessing zone, and the hydrogenation catalyst is preferably added at a rate sufficient to suppress coke formation in the first stage hydroprocessing zone, and this amount is determined by routine experimentation for the particular equipment. When coal or coal-containing particles are added to the feed, which can be easily measured by In order to prevent the buildup of minerals in the system, it is preferable to remove at least some of the minerals before recycling the heavy liquid. Examples of suitable methods 6. The liquid product from the sieve separator 40 exits through line 55 and enters the solids separation zone 100, which is a settler and filter.

A centrifuge, ]-hydrochron, etc., can be used to obtain a solids-rich stream 103 and a solids-poor stream 105.

A part of the flow with less solids is transferred to line 90'3F (I
Press L to cycle through the ladle. As previously mentioned, the light liquids can be removed by fractionation or flushing prior to filtration of the remaining liquid.

Solids σ) Minor stream 105 or a portion thereof is optionally treated in a secondary solids separation zone. The solid-rich part of 7c is drained through 112 lines. The solids-poor portion 115 is divided into fraction 8 in the rectification zone 85.
6.87, 88 and 89 were separated. If desired, all or a portion of one heavy fraction can be pumped to the feed zone 20 or elsewhere. coal and solid coal containing coal;
It may be added to the feed in amounts of 1 to 50 kg per 100 kg of oil feed.

EXAMPLE 1 Referring again to FIG. 1, a heavy hydrocarbon oil, such as petroleum vacuum distillation residue, was prepared by dispersing an aqueous ammonium butamolypdate solution and a fuel oil in line 5. , line 10 and mix with the emulsion added. The amount of molybdenum in the emulsion is
As molybdenum metal per gram (Co OO
05 to 0.005 kg, preferably 0.0002 to 0.05 kg.
The prefecture is large enough to be ranked 0007k17. The feed containing the dispersed catalyst enters the first stage hydrogenation zone 20 where it is heated to a temperature of 400-450°C.
200 atm pressure, 150-190 atm hydrogen pressure.

1500~1800##! Feed and skin contact with hydrogen at a residence time of 5 to 2 hours. Hydrogenation zone 20 is an up blow vessel with a packed bed of acpargite clay.

All effluent from hydrogenation zone 20 enters second hydrogenation zone 30 through conduit 25.

The second hydrogenation zone 30 will preferably be an upflow vessel having a fixed bed of hydrogenation catalyst consisting of cobalt, molybdenum and phosphorous on a gamma alumina support. Temperatures lower than one step, and temperatures within the range of 660-400'O, 170-2
00 atm pressure, residence time of 1-5 hours and 150-
It operates at a hydrogen pressure of 190 atm. Second hydrogenation zone 3
The effluent from 0 passes through conduit 35 to high pressure separator 40 where it is treated for hydrogen gas enriched recycle gas removal and acid gas removal, and line 50;
1 ↓ to circulate PI 8 2°C4-hydrocarbon gas flow.

The normally liquid product is recovered through line 45 and line 55. Some of that liquid product? , through line 60 to rectifier 85.

The rest of the hV body products are recycled through line 90). The +T) chain ring portion is a full boiling range liquid (C5-4-) or a relatively high boiling fraction, such as 200"C+ or 550"C+.

The r+】circulation f■ part is den! In terms of
j−Z+. 05+ product total boiling range portion of zone 30? In the case of FJ circulation (engineering, supply γ++'ky 95 ~
100kg'f Fj circulates.

Referring to Figure 6 of Example 6, a heavy oil such as petroleum residue is added to the slurry zone (not shown) through line 12. 30 of
Mix with the mesh pass portion).

The coal to residual oil ratio is 0 coal per 100 kliJ of residual oil feed, 50 coal per 0 kg ICl of residual oil feed.
scales that can vary up to kg or more
: Enters the I-1 first hydrogenation treatment zone 20. here,
Externally supplied catalysts or contact particles are preferred. In zone 20, the temperature at 175°C is 400-450°C, the pressure is 170-200 atm, and the hydrogen pressure is 150-190 atm.

1500-18007? /e Feed hydrogen feed 9 and contact with hydrogen at a residence time of 0.5 to 2 hours.

The total effluent from zone 20 is transferred to the second hydrogenation zone 3.
Enters 0. Is this Gammaa? It is an upflow vessel with a fixed bed of hydrogenation catalyst consisting of cobalt, vanadium and phosphorous on a remina support. This second hydrogenation zone 30 is 6. Preferably a temperature of 360-400°C,
It operates at a pressure of 170-200 atmospheres, a residence time of 1-5 hours and a hydrogen pressure of 150-190 atmospheres. The effluent from the second hydrogenation zone 30 enters the high pressure separator 40 through conduit 35 where hydrogen-rich recycle gas is removed and recirculated through line 50 in gaseous form. The hydrocarbon stream is recovered via line 45. The normally liquid product plus ash and undissolved Vf (stone enters separator 100 through line 55). A portion of the solids-poor stream 105 is recycled through line 90. Is only the C5+ full boiling range stream recycled through line 90? The ratio of residual oil to 4 oil feed is 9 to 10 residual oil (5 to 10 per 100 kg of feed).
0 kg 0 town circulation oil is preferable.

Regardless of whether contact particles or suspended catalysts are used, the conditions within the hydroprocessing zone and the composition of the recycled soil can be varied within approximately the limits described herein. It will be appreciated by those skilled in the art of petroleum processing that the present invention may be practiced in various embodiments other than those specifically described herein without departing from the spirit and scope of the invention. Such embodiments as may be realized are considered equivalent to those described herein and as claimed.

[Brief explanation of drawings]

1M is a flow diagram showing the method of the present invention when no solid substance is added. FIG. 2 is a flow diagram illustrating the method of the present invention when porous negative metal getter particles are added. FIG. 6 is a flow diagram illustrating the method of the present invention when one coal or coal particles are added. Agent Akira Asamura

Claims (1)

Claims: In a process for hydrotreating a heavy hydrocarbon oil feed containing liquid components boiling above fi+ 500'C. In a first reaction zone, said oil feed is contacted with hydrogen under hydrogenation conditions comprising a hydrogen pressure greater than 65 atmospheres to form a first liquid effluent comprising a liquid component having a boiling point greater than 500°C. in a second reaction zone, under hydrotreating conditions in the presence of a hydrogenation catalyst, at least a portion of said first effluent containing a liquid component with a boiling point above 500°C. contacting said portion of said second effluent with hydrogen to produce a second effluent comprising a liquid component boiling above 500°C; A method for hydrotreating a heavy hydrocarbon oil feed as described above, characterized in that said heavy hydrocarbon oil feed is recycled to said first reaction zone. 2) The hydrotreating conditions in the first reaction zone include a temperature in the range of 650 to 500°C, a pressure in the range of 40 to 680 atm, a residence time in the range of 0.1 to 10 hours, and 355-35501/j the hydrogen gas supply of the feed, and said hydrotreating conditions in said second reaction zone are lower than the temperature in said first reaction zone, and 61
temperature within the range of 5 to 455 °C, pressure within the range of 40 to 640 atm, space velocity within the range of 0.1 to 27 h, and 170 to 5400 (including hydrogen feed rate of 1/l feed). The method of paragraph 1. (3) said hydrocarbon oil feed or at least about 1
2. The method according to claim 1 or 2, further comprising a liquid component having a boiling point higher than 500° C. and having a boiling point of 0% by weight. (4) The method according to item 1 or 2, wherein the catalyst in the second stage is present in an ebullated bed. (5) The method according to item 1 or 2, wherein the second stage catalyst is present in a packed bed. (6) The method according to item 1, wherein the catalyst in the second stage comprises a hydrogenation component selected from Groups VIB and Vl11 of the Periodic Table on a support consisting of Al2O3. (7) The first hydrogenation zone or porous contact particles? The method according to item 1 above, comprising: (8) said recirculated g, portion is 11/at least 5% by weight;
said first component containing a component having a boiling point higher than 500'C of
The method according to item 2 or 7. ]9) Does the recycle portion contain at least about 10 parts by weight of components boiling above 500'O? The first to containing
The method according to item 2 or 7. In a process for hydrotreating a hydrocarbon oil feed containing a liquid component with a boiling point higher than 1500 °C (al) in the presence of externally fed porous contact particles in the first reaction zone. The pre-Me oil feed is contacted with hydrogen under hydrogenation conditions including the presence of at least 35 atmospheres of hydrogen to produce a first effluent containing a liquid component boiling above 500°C. tJ) of said first effluent under hydrotreating conditions in the presence of a hydrogenation catalyst.
(Both a part containing a liquid component with a boiling point higher than 500°C and at least a part of said contact particles are brought into contact with hydrogen, and a second part containing a liquid component with a boiling point higher than 500°C producing an effluent; A method for hydrotreating said Juga hydrocarbon oil feed, characterized in that said recirculating portion of said second effluent or at least a portion of said contact particles is recycled to said first reaction zone. +12) The hydrogenation conditions in the first reaction zone include a temperature within the range of 350 to 500 C;
said hydrotreating method in the second reaction zone operating a pressure in the range of 0 to 680 atmospheres, a residence time of 0.1 to 6 hours and a hydrogen gas feed rate of 655 to 5550 l/l feed; lower than the temperature of the first reaction zone of
or paragraph 10 above, comprising a temperature in the range of 615 to 455°C, a royal power in the range of 40 to 340 atmospheres, a space velocity in the range of 0.1 to 27 hours, and a hydrogen supply location of 170 to 3400171 feed; The method described in Section 11. F131 The method of paragraph 10, wherein said hydrocarbon feed comprises: 11) a liquid component having a boiling point above 500° C. of at least about 10M. The method according to item 10, wherein the catalyst in the second stage is present as a packed bed. (15) The method according to item 10, wherein the catalyst in the second stage is present as a packed bed. (16) The catalyst in the second stage is present as a packed bed. , !VIB and V111;
11. The method of claim 10, wherein the method is supported on a refractory oxide consisting of 103. (1) The method according to item 10, carried out in the presence of the hydrogenation catalyst and the dispersed hydrogenation catalyst in the first reaction zone. 10. The method according to paragraph 10 above, wherein the recirculation 7'ili minutes are <J> at least 5.
The method according to the above-mentioned item 10, l'i, which contains a component with a boiling point of 500'O to T#, which is a heavy needle. (2(ll) The method according to item 10 above, wherein the recirculation process 1. ) In a method for liquefying coal and hydrotreating heavy hydrocarbon oils containing liquid components with a boiling point higher than 500° C. (at forming a slurry consisting of said coal (IZ hydrogen oil and said coal); and in a first reaction zone, said slurry is contacted with hydrogen under hydrogenation conditions operating at a hydrogen pressure of at least 65 atmospheres to remove undissolved solids and liquid components boiling above 500°C. (b) Hydrotreating in the presence of a hydrogenation catalyst in a second reaction zone, at least a portion of said first effluent, a liquid having a boiling point higher than 500'C! (4) contacting said portion with hydrogen to form a second effluent containing undissolved solids and liquid components boiling above 500°C; characterized in that at least a portion (this portion containing substantially all of the liquid components boiling above 500'C) is recycled to the first reaction zone. Method. (22) said recirculated portion of said second effluent comprises:
@2 containing at least a portion of the undissolved solids
The method described in Section 1. E(l of the hydrocarbon feed, at least about 10
22. The method according to item 21, wherein the liquid component has a boiling point higher than 500''C. cl! ■ The method according to paragraph 21, wherein the catalyst of the second stage is present as a packed bed.
containing hydrogenated components such as from the group Al2O-4
22. The method of claim 21, wherein the method is supported on a refractory oxide comprising: (211) The method of claim 21, wherein said hydrogenation in said first reaction zone is carried out in the presence of a dispersed catalyst. The 21st component contains a component with a boiling point higher than C.
The method described in section. CI! 9) said recirculating portion or at least about 10
22. The method according to item 21, which comprises an open-mold I3y' having a boiling point higher than 500"G.