FR2540883A1 - PROCESS FOR HYDROCRACKING HEAVY OILS IN THE PRESENCE OF DRY MIXTURE ADDITIVE FORMED OF COAL OR SCARBLES AND A METAL COMPOUND - Google Patents

Abstract

A PROCESS FOR THE HYDROCRAQUAGE OF HEAVY HYDROCARBONOUS OILS, SUCH AS OILS EXTRACTED FROM TAR SANDS, IS DESCRIBED. THE OIL INTRODUCED IN THE PRESENCE OF AN EXCESS HYDROGEN IS SENT THROUGH A TUBULAR HYDROCRACKING ZONE 13, AND THE EFFLUENT FROM THE TOP OF THE ZONE IS SEPARATED INTO A GAS CURRENT CONTAINING A WIDE BOILING RANGE MATERIAL AND A LIQUID CURRENT CONTAINING HEAVY HYDROCARBONS; ACCORDING TO THE INVENTION, THE HYDROCRACKING PROCESS IS CARRIED OUT IN THE PRESENCE OF AN ADDITIVE CONSISTING OF FINALLY DIVIDED COAL OR OTHER CARBON MATERIAL, DRY MIXED WITH CATALYTICALLY ACTIVE METALS SUCH AS IRON, COBALT, AND MOLYBDENE . THE ADDITIVE IS MUDDED WITH THE MATERIAL INTRODUCED AND IT WAS FOUND THAT THIS WAS GREATLY REDUCED COKE PRECURSORS AND THUS PREVENTS THE FORMATION OF CARBON DEPOSITS IN THE REACTION ZONE, WHILE BEING ALSO EFFECTIVE IN REDUCING THE CONCENTRATION OF THE COKE. .

Description

1. The present invention relates to treatment

  hydrocarbon oils, and more particularly,

  cracking of heavy hydrocarbon oils to provide

  improved products with a lower boiling range.

  Hydrocracking processes for the transformation

  heavy hydrocarbon oils in inter-naphtha

  good quality light and medium for reforming feed materials, fuel oil and gas oil are well known These heavy hydrocarbon oils can be materials such as crude oil, base products

  (or tail) of tars subjected to atmospheric distillation

  spherical, bottom (or tail) products of tar subject to vacuum distillation, heavy cycling oils, shale oils, and liquid oils from coal, crude oil residues, crude oils headless, and heavy bituminous oils extracted from oil sands Oils extracted from oil sands and which contain materials with a wide boiling range, ranging from naphthas to kerosene, gas oil, pitch, etc. and which contain a 2 o large part of matter-boiling above 524 C,

  equivalent boiling point under atmospheric pressure

  particularly interesting.

  Heavy hydrocarbon oils of the above type

  above tend to contain nitrogen and sulfur compounds in excessively high concentrations In addition,

  these heavy hydrocarbon fractions frequently contain

  excessive amounts of contaminated products

  organometallic tends to be extremely no-

  cives vis-à-vis various catalytic processes which can-

  can be subsequently made, such as hydropurification

  cation Among the metallic contamination products,

  those containing nickel and vanadium are the most common

  rants, although other metals are often present.

  These metallic contamination products, as well as

  very, are usually present in the bituminous matter

  in the form of relatively high molecular weight organometallic compounds A considerable amount of the organometallic complexes is bound to the asphaltenic material and contains sulfur Of course, in the

  catalytic hydrocracking procedures, the present

  that large amounts of asphaltene and organometallic compounds interfere considerably with

  the activity of the catalyst with respect to the removal of

  of nitrogenous, sulfur and oxygenated compounds A bitu-

  me typical of Athabasca can contain 51.5% by weight of material boiling above 524 C, 4.48% by weight of sulfur, 0.43% by weight of nitrogen, 213 ppm of vanadium and

E 7 ppm nickel.

  While conventional crude oil reserves

  as they decrease, these heavy oils can be upgraded to meet demand. In this upgrading, the heavier material is transformed into lighter fractions and most of the sulfur, nitrogen and

metals must be removed.

3.

  This can be achieved by a coke-

  faction such as delayed or fluidized coking, or

  by a hydrogen addition process such as hydro-

  catalytic or thermal cracking The distillation yield

  lat from the coking process is about 70% by weight and this process also provides about 23% of

  coke as a by-product which cannot be used as

  burns me because of the low hydrogen: car-

  bone, and the high content of sulfur and mineral products

  According to the operating conditions, the hydrogenation processes can give a distillate yield

more than 87% by weight.

  Recent work has been done on a treatment route as a variant involving the addition

  of hydrogen at elevated temperatures and pressures

  and we found it to be very promising In this process, hydrogen and heavy oil are pumped up through an empty tubular reactor in the absence of any catalyst We found that the compounds by weight high molecular hydrogenate and / or are subjected to hydrocracking to provide lower boiling ranges Simultaneous desulfurization, demetallization and nitrogen removal reactions take place

  reaction pressures up to 24 M Pa and temperatures

  erasures up to 490 ° C were used.

  In thermal hydrocracking, the im-

  bearing is the depot of coke or solid in the reactor, especially when operating at relatively pressures

  low, and this can result in costly outages

  its Deposits are formed at the top of the reactor where the partial pressure of hydrogen and the ash content are at the lowest. Higher pressures reduce the fouling of the reactor At 24 M Pa and at 4700 C, the coke deposit can be later eliminated However, operating industrial plants at high pressures involves operating costs

and-from upper hospitals.

  It has been well established that the mineral matter pre-

  feeling in the feed material plays an important role

  both in the Chervenak et al.

  in U.S. Patent No. 3,775,296 show that the ma-

  foodstuff containing a high content of pro-

  mineral product (3.8% by weight) is less likely to form coke in the reactor than the feed containing a

  low mineral content (<1% by weight)

  very studies have shown that a high mineral content had no apparent effect on the transformation of the pitch and the desulfurization, but it suppressed the deposit of coke in the reactor and the general fouling of the

reaction.

  It has also previously been shown that the deposit of coke in the reactor can be eliminated by recirculating a portion of heavy end products to the lower part of the reactor zone. In US patent 3,884,937, it has been shown that , when the concentration of mineral product in the reactor fluid

  was maintained between 4 and 10% by weight during the hydro-

  thermal cracking, there was no coke in the

  reactor It appeared that during the hydro-

  cracking, the carbonaceous material was deposited on particles

  solids instead of being on the reactor wall and

  could thus be transported outside with the ef-

  reactor fluent This indicated the possibility of adding

  ter and continuously remove a coke carrier in the

reactor.

  The addition of coke carriers has been proposed

  in U.S. Patent 3,151,057 which suggested the use of

  Use of "capture products" such as sand, quartz, alumina, magnesia, zircon, beryl or

  bauxite These "capture products" could be regenerated

  res after use by heating the soiled support with oxygen and water vapor to about 10,900 C to provide regeneration gases containing a substantial amount of hydrogen Qn shown in Canadian patent NO 1 073 389 and in the U.S. patent

  cain N O 4 214 977, that the addition of coal or cat-

  charcoal lyser causes reduction of coke deposition during hydrocracking Charcoal additives serve as locations for deposition of coke precursors and thus provide a mechanism for removal at

from the device.

  The use of these char catalysts

  good allows to operate at lower pressures and

  with higher conversions The use of cataly-

  charcoal and Co, Mo and Al catalysts on charcoal is described in Canadian Patent No. 1,073,389, the use of iron-charcoal catalysts in

  U.S. Patent No. 4,214,977 and the use of pressure ulcers

  beads in Canadian Patent No. 1,124,194.

  U.S. Patent No. 3,775,286 describes a process for hydrogenating coal, where the coal has been impregnated with hydrated iron oxide or dry hydrated iron oxide powder has been physically mixed.

  with powdered charcoal However, the levels of

  version using a physical mix were very niau-

  go by comparison with impregnated charcoal.

  It is the object of the present invention to use

  be an inexpensive, removable, carbon-based additive in a heavy hydrocarbon feedstock to overcome some of the problems of deposits being formed

  in the reactor during the hydrocracking process.

  The present invention relates to a process for subjecting hydrocracking to a heavy hydrocarbon oil, a substantial part of which boils above

  5240 C, o a mud of heavy hydrocarbon oil and approxi-

  ron 0.01 25% by weight of carbonaceous particulate additives

  in the presence of 90 9000 m of hydrogen / m of hydro-

  carbonaceous are caused to pass through a hydro-

  enclosed cracking The hydrocracking zone is maintained at a temperature between about 375 and 500 WC under a

  pressure of at least 3.5 M Pa and at a space speed (de-

  bit) up to 4 volumes of hydrocarbon oil per hour per volume of hydrocracking zone capacity A mixed effluent containing a gas phase comprising lo and hydrogen and hydrocarbons in the vapor state and a liquid phase comprising heavy oil is

  removed from the hydrocracking zone, and the effluent is separated

  re in a gas stream containing hydrogen and hydrocarbons in the vapor state and in a liquid stream containing heavy hydrocarbons According to a new characteristic, the additive particles used are in the form of a dry mixture of ground coal or other

  carbonaceous matter and a ground metal salt.

  This process substantially prevents the formation of carbonaceous deposits in the reaction zone. These deposits, which may contain organic materials insoluble in benzene and quinoline, inorganic materials,

  metals, sulfur, and poorly soluble organic materials

  benzene, will be referred to below as

name of "coke" repositories.

  Of course, the dry mix is much cheaper to produce than ordinary additives impregnated with

  metallic salts At the same time, it compares favorably-

  additives impregnated for the reduction of precur-

  coke sisters and the prevention of deposit formation

of coke in the reaction zone.

  The process of the present invention is particularly

  particularly well suited for the treatment of heavy oils having

  a large proportion, preferably at least 50% by vo-

  lume, which boils above 5241 C and which can contain a 7. wide boiling range for materials ranging from naphtha to kerosene, gas oil and pitch It can be operated under very moderate pressures , preferably in the range of 3.5 to 24 M Pa

  without formation of coke in the hydrocracking zone.

  Although hydrocracking can be carried out in a large number of known flow reactors

  ascending or descending, it is particularly well suited

  tee to a tubular reactor through which the feed

  tion and the gas move upwards The effluent pro-

  coming from the top is preferably separated in a separa-

  hot gas stream from the separator

  hot can be sent to a high pressure separator-

  low temperature where it is separated into a gas stream

  containing hydrogen and lesser amounts of hydro-

  gaseous carbides and in a stream of liquid product contained

the light oily product.

  The metal compound that is used for the ad-

  ditif is a compound that turns into a metallic sulfide

  that from the action of hydrogen and sulfhydri-

  that it can be a metal oxide, a metal salt such as a sulfate, a sulfide, a chloride, a fluoride,

  a nitrate, an oxalate or a carbonate or a hydroxide

  metal The metal is typically a catalytically active metal such as iron, cobalt, nickel, molybdenum, chromium, tungsten, vanadium, zinc, etc. A

  a particularly preferred compound is iron sulfate.

  The metal salt and carbonaceous material used

  according to the present invention are preferably at least

  very small particle size, for example passing through a sieve with a mesh size of less than 246 µm (60 mesh) and it is particularly preferred to use a material

  which will pass through a sieve with an open mesh

  smaller than 147 pm (100 mesar) Nevertheless, it is possible to obtain the advantages of the present invention with

254 0883

  8. larger particle sizes up to 6.35 mm a typical additive mixture S will contain 5 to 95% by weight of metal salt and usually the catalyst

  is mixed with the heavy oil supply in quanti-

  0.1 to 5% by weight, based on heavy oil supply, although it can vary as widely

  between 0.01 and 25% by weight, based on the feed

  tation. The additive can conveniently be prepared in

  grinding, drying and subsequently sifting a char-

  good suitable up to a size passing through a sieve with a mesh opening of 147 µm (100 mesh) A calculated amount of metal salt passing through a sieve with a mesh opening of 147 µm (100 mesh) is slowly added to the carbon in a device transformation into dough by mixing and the batch is mixed for approximately

  minutes Some metal salts must be dried

  before sieving to pass through mesh with an opening of 147 pm (100 mesh), in order to decrease hydroscopy by reducing the hydrate water content or the humidity The drying can suitably be carried out at around 900 ° C. for 3 hours Reduced hygroscopy

  Slowly facilitates subsequent passage through the sieve.

  Particle sizes can be smaller

  greater than 147 pm (100 mesh) depending on the geometry

  reactor sorting and coking trends of the

  feed material formed from heavy hydrocarbon oil

  The dry mixing procedure thus allows the

  particle size of metal salts and at the

  Coal size to be set independently For example, the size of carbon particles should be chosen larger to obtain a longer residence time for these particles, which would allow more liquefaction. It has been found, according to the present invention, that particularly good results are obtained when

  the metal salt is mixed with charcoal, preferably

  Lignite or sub-bituminous or mixed coal

with carbuncles.

  Coal can broadly be defined as

  being a mineral substance consisting of organic matter

  carbonaceous There are many different types of coal, including lignite, bituminous coal and

  anthracite Lignite is a material with a character

  intermediate between peat and coal and contains a substantial proportion of volatile hydrocarbons Bituminous coal is the most common type of coal

  and is somewhat harder than lignite, with a te-

  higher carbon content and lower volatile hydrocarbon content Sub-bituminous coal is a material of intermediate character between lignite and bituminous coal Anthracite is a very hard coal, containing a high proportion of carbon and a very low proportion of volatile compounds On the other hand, coke is the solid product of the action of heat on coal and consists of a hard, porous mass,

  carbon containing very few volatile compounds.

  In the present process, the additive is specified

  only used to suppress coke formation and

  to remove coke deposits So we found it parti-

  particularly advantageous to mix the metal salt with

  lignite or sub-bituminous coal or carbuncles

  them instead of coke or semi-coke For example, we have

  observed that, under hydrocracking conditions, the li-

  gnite significantly hydrogen and coal

  bituminous, coke or semi-coke are the least hydrogenated.

  The importance of hydrogenation of sub-bituminous coal

  neux is between the extremes above So a catalyst support & hoe condition ideal for this process

  hydrocracking must partially hydrogenate, between P-

  10. resulting in a reduction in particle size and these particles must leave with the product stream, taking away some of the deposited coke For the reasons

  above, it will also be clear that a sup-

  wearing coke or semi-coke for this purpose is not satisfactory.

  According to a preferred embodiment, the ali-

  ment of heavy hydrocarbon oil and the metal additive

  coal are mixed in a feed tank and

  pumped with hydrogen through a vertical reactor.

  The liquid-gas mixture from the top of the hydrocracking zone can be separated in a number of different ways. One possibility is to separate the liquid-gas mixture in a hot separator maintained

  between 200-470 C and under the pressure of the hy-

  cracking The product formed of heavy hydrocarbon oil from the hot separator can be recycled or sent

secondary treatment.

  The gas stream from the hot separator

  containing a mixture of gas and hydrocarbon and hydro-

  gene is still cooled and separated in a separator under high pressure at low temperature Using this

  type of separator, the output gas stream obtained con-

  is mainly hydrogen with certain impurities-

  tees such as hydrogen sulfide and light gaseous hydrocarbons This gas stream is passed through

  a scrubber and the purified hydrogen is recycled as-

  part of the hydrogen supply to the hydrocracking process The purity of the recycled hydrogen gas is

  maintained by regulating the purification conditions and adding

so much make-up hydrogen.

  The liquid stream from the low temperature-high pressure separator represents the light oily hydrocarbon product of the present process and can be

  sent to secondary treatment.

  Part of the metal-coal additive will be transported with the heavy oily product from the hot separator and will be in the pitch fraction at 5241 C + However, since it is a very cheap additive, it does not need to '' can be recovered and can be burnt or carbonated with pitch The concentration of metal-carbon additive in the feed is normally between

  0.1-5.0% by weight, preferably about 1.0% by weight.

  Under hydrocracking conditions, metal salts

  are transformed into metallic sulphides.

  To better understand the present invention, reference is made to the accompanying drawing which illustrates schematically

  a preferred embodiment of the present invention

  tion. A supply formed of hydrocarbon oil

  heavy and a metal salt-coal additive are mixed

  placed in a feed tank 10 to form a

  mud This mud is pumped through the pump

  feed pe 11 through the inlet pipe 12

  to the bottom of an empty tower 13 Hydrogen recy-

  key and make-up hydrogen from the pipeline

  tion 30 are simultaneously sent into the tower by the

  end of line 12 A gas-liquid mixture

  de is removed from the top of the tower via line 14 and introduced into a hot separator In the hot separator, the effluent from the

  tower 13 is separated into a gas stream 18 and a cou-

  rant liquid 16 The liquid stream 16 is in the form

  heavy oil which is collected in 17.

  According to one characteristic, as a variant, a diversion pipe is connected to pipe 16. This bypass pipe establishes a connection

  through a pump, into the canali-

  input station 12, and serves as recycling to recycle the stream of liquid containing particles of sulfide f 2 54 X 03 o 12.

  transported metal and coal fines from

  from the hot separator 15 into the feed mud

tower 13.

  In another exemplary embodiment, however, the line 16 feeds into a cyclone separator which separates the metal sulfide particles and the carbon fines from the liquid stream The separated metal sulfide particles and the fines

  coal are recycled in the feed sludge until

  only in tower 13, while the remaining liquid is returned

in container 17.

  The gas stream from the separator 15 is

  transported by means of line 18 in a separa-

  high pressure-low temperature 19 In this separator

  erator, the product is separated into a hydrogen-rich gas stream which is withdrawn through line 22, and an oily product which is removed through line

and gathered in 21.

  The stream 22 rich in hydrogen is sent via a packed purification tower 23 where it is purified by means of a purification liquid 24 which is recycled via the tower by means of the pump 25 and the recycling loop 26 The purified stream rich in hydrogen emerges from the purifier via

  line 27 and is combined with hydrogen from ap-

  fresh point added via line 28 and recycled via gas pump 29

  recycling and pipeline 30 to tower 13.

  Certain preferred embodiments of the present invention will now be further illustrated by

  the following nonlimiting examples.

* EXAMPLE 1

  An additive was prepared by grinding and sieving

  sant a sub-bituminous coal until it passes through a sieve with a mesh opening of 74 pm (200 mesh). This material 13 was subsequently mixed with a quantity

  predetermined iron sulfate and dried, crushed and sieved

  seated to a size passing through a sieve with a mesh opening of 74 µm (200 mesh) The iron sulfate was first dried because it occurs under normal conditions as a heptahydrate, to say

  Fe SO 4 7 H 20 This salt is hygroscopic and forms agglomerates.

  res which block the sieve openings The heptahydrate was dried to the monohydrate form Fe SO 4 H 20 by

  heating up to 90 C for about 3 hours The sulfa-

  te of dried iron was then ground and sieved It was

  slowly added to the coal in a forming device

  tion of dough by mixing and mixing for approxi-

  10 minutes The resulting mixture was placed in

  a drum and rotated for about 4 hours

  res. The properties of the dry mixed additive are

  presented in table 1 below with the properties

  of a typical impregnated additive.

TABLE 1

  Analysis of dry mixed and impregnated additive Dry mixed Impregnated Solder% by weight 4.81 4.72 Ash% by weight 21.76 20.8

Products in% by weight 93.6 -

  soluble in pentane Products in% by weight 93.0 soluble in toluene Vanadium ppm 180 79 Nickel ppm 72 119 Iron% by weight 8.78 8.96 Carbon% by weight 41.31 41.05 Hydrogen% by weight 2, 97 3.06 Nitrogen% by weight 0.51 0.50

2 .; 403,

  14. The distribution of dimensions of the two additives

rnnàe in table 2.

YOUR BLUE U 2

  Analysis with a dry sieve of the dry-mixed add-tf and 3 of the impregnated additive 1 Retained in a sieve with 74 Vm mesh opening

  The feed material used was a

  vacuum distillation sidu known as Cold Lake 3 having the following properties:

TABLE 3 -

  Properties of the feed material known as Cold Lake DIè-si t Density Sulfur Ash

C.C R.

  Products insoluble in pentane Products insoluble in toluene Asphaltenes Carbon Hydrogen Nitrogen Vanadium Nickel Iron Sediment (extraction) Water (distillation) Pitch 2 A Pl

/ 15 C

  l% by weight% by weight% by weight% by weight% by weight% by weight% by weight% by weight% by weight ppm ppm ppm% in% in% by weight weight weight Additive I Dry mix Impregnated imn Weight Yield Weight Yield (grams) t%) (grams) (%)

147-74 5.17 2.5 4.66 2.91

74-43 48.35 23.0 42.38 26.4

<43,156.43 74.5 113.51 70.7

  4.8 1.038, 82 0.05 19.8 22.7 0.07 22.6 82.90 9.96 0.68 trace trace, 10

2540 33

15.

1 Carbon residue known as Conradson.

  2 Boiling material above 524 C.

  3 A region in western Canada.

  A mixed slurry of the above feed material and 1% by weight of the dry mixed additive was prepared and this slurry was used as the material

  supply to a hydrocracking installation,

  illustrated me in the attached drawing.

  The reactor was operated under the conditions

  following reactor versions: Reactor temperature C 450 Pressure M Pa 13.9 Hourly space velocity (flow) of liquid 0.75 Rate of recycled gas m 3 / h 5.9 Purity of recycled gas (hydrogen)% by volume 85 Length of test h 422 The results obtained from this test were as follows: Conversion of pitch (524 "C +)% by weight 87.5 Conversion of sulfur% by weight 65.5 Yield in liquid product (C 4 +) % by volume 106.1 Product yield _ liquid (C 4 +)% by weight 92.7 C gas 1 C 3% by weight 5.7 Hydrogen consumption m 3 / tonne 221.9

  At the end of the test, 143 grams of soil deposits

  lides were found in the device.

  The results can be compared to a test in which an impregnated charcoal-iron additive was

  employee A light Cold Lake feed material

  quite different has been used: its properties are given below: 16.

TABLE 4

  Properties of the so-called feed material (used with the impregnated additive) Cold Lake Densite Sulfur Ash

C.C R.

  Products insoluble in pentane Asphaltenes Products insoluble in toluene Carbon Hydrogen Nitrogen Vanadium Nickel Iron Viscosity

Viscosity -

Pitch

/ 15 C

  % by weight% by weight% by weight% by weight% by weight% by weight% by weight% by weight% by weight ppm ppm ppm Centistokes at 82 o C Centistokes

at 99 C

  % by weight For this test, the operating conditions were as follows: Reactor temperature o C 448 Pressure M Pa 13.9 Hourly space velocity (flow) of liquid 0.75 Rate of recycled gas m 3 / ton 5, 9 Purity of the recycled gas (hydrogen)% by volume 85 Test length h 513 1.026, 16 0.064 18.2 21.0 21.0 0.03 82.93, 29 0.57 72.95 iii 1 - i I i 17 The following results were obtained: Pitch conversion% by weight 85.5 Sulfur conversion% by weight 55.9 Yield in liquid product (C 4 +)% by volume 102.7 Yield in liquid product (C 4 +) % by weight 92.3 C 1 -C 3 gas 3% by weight 5.1 Hydrogen consumption m 3 / ton 196.8 The total quantity of solids deposited during this test was 72 grams, which compares favorably

  to the 143 grams of solids deposited in the additive test

  dry mix tif Tests under the same operating conditions with no metal-carbon additive present could only be operated for a short time, before excessive deposit formation or before clogging occurred. test

  with Athabasca bitumen at 450 C with a speed spa-

  hourly rate (flow) of liquid greater than 3.0, without additives, provided 6600 grams of deposits after

384 hours.

  The properties of Athabasca bitumen, the conditions

  operating conditions and the results for this trial are

given below.

  Properties of Athabasca 'bitumen -

  Density 15/15 C 1.009 Sulfur% by weight 4.48 Ash% by weight 0.59 Carbon residue Conradson% by weight; 13.3 Products insoluble in pentane% by weight 15.5 Products insoluble in benzene% by weight 0, 72 Vanadium content ppm 213 Nickel content ppm 67 Total acid number Mg KOH / g 2.77 18. Total base index Carbon Hydrogen Nitrogen (Microcoulometer known as Dohrmann) Chlorine Viscosity Pitch (524 C) M A region of tarry west. Operating conditions Amount of additive Pressure Reactor temperature Length of test Hourly space velocity (flow) of liquid Rate of recycle gas Purity of

recycling (hydro-

  Results): Pitch conversion Sulfur conversion Hydrogen consumed Yield in liquid product Yield in liquid product

Solid deposits to-

  rate in the device mg of K Oa / g% by weight% by weight% by weight% by weight Centistokes at 38 C% by weight of Canada containing sands% by weight M Pa o C * hm 3 / h -% by volume % by weight% by weight m / ton% by volume% by weight g We can clearly see from these results that

  iron-carbon additives are very effective in preventing

  expensive deposition of solids - Additives dry mixed and 1.89 83.36, 52 0.43 0.00 51.5 o O, 44 3.0, 6, 6 29.9 58.2 94.2 impregnated had coke removal activities

roughly equal.

  The appreciation of some of the measurement values

  res indicated above must take into account the fact that they come from the conversion of Anglo-Saxon units into

metric units.

  The present invention is not limited to the examples

  ples of realization which have just been described, it is on the contrary susceptible of variants and modifications

  which will appear to those skilled in the art.

20.

Claims (10)

  1 Process for submitting to hydrocracking   a heavy hydrocarbon oil, a substantial proportion of which   tantielle boils above 524 C, in which we do not-   ser a slurry of this heavy hydrocarbon oil and a carbonaceous additive, in the presence of 90-9000 m 3 of hydrogen / m 3 of hydrocarbon oil through an enclosed hydrocracking mine, this hydrocracking zone being maintained at   a temperature between about 375 and 500 C, at a pressure   sion above 3.5 M Pa and at a space speed (flow) of up to 4.0 volumes of heavy hydrocarbon oil per hour per volume of hydrocracking zone capacity;   a mixed effluent, containing a compressed gas phase   nant of hydrogen and hydrocarbons in the vapor state and a liquid phase comprising heavy hydrocarbons is removed from the hydrocracking zone; and the effluent is separated into a gas stream containing hydrogen and hydrocarbons in the vapor state, and into a liquid stream containing heavy hydrocarbons, characterized   in that the carbon additive is a mixed powder obtained   naked by intimately mixing dry particles of coal or carbuncles and dry particles of a metallic compound.   2 Method according to claim 1, character-   dried in that the coal is lignite or coal under bituminous.   3 Method according to claim 2, charac-   se in that the metallic compound is a compound which transforms into metallic sulfide under the conditions of reactor.   4 Method according to claim 2, character-   dried in that the metal compound is a metal salt.   Method according to claim 4, characteristic   se in that the metal compound is a catalytic metal   cally active chosen from iron, cobalt, nickel, 21. molybdenum, chromium, tungsten, vanadium and zinc. se in se in se in weight se in addi   6 Method according to claim 5, character-   what the metal compound is an iron salt.   7 Method according to claim 6, character-   what the iron salt is iron sulfate.   8 Method according to claim 1, character-   what the mud contains about 0.01 25% in of the additive.   9 Method according to claim 8, character-   that the mud contains 0.1 5% by weight of tif.   Method according to claim 2, characteristic   dried in that the additive particles pass through a sieve   246 µm (60 mesh) mesh opening.   11 Method according to claim 1, character-   dried in that the carbonaceous additive is formed from carbuncles.   12 Method according to claim 11, character-   risé in that the metallic compound is a compound which transforms into metallic sulfide under the reaction conditions.