NL8402008A - METHOD FOR CONVERTING HEAVY HYDROCARBONS INTO MORE VALUABLE PRODUCTS - Google Patents

Description

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l i 1 * * .. -1- t VO 6317

Process for converting heavy hydrocarbons into more valuable products.

The invention relates to a method for converting heavy hydrocarbons, in particular a heavy oil, such as an atmospheric residual oil or a vacuum residue of crude oils, into lighter and more valuable products, as well as a method for further hydrotreating the lighter hydrocarbon oil, which also includes a process for preparing gaseous olefins and monocyclic aromatics from a heavy hydrocarbon, which is the feedstock in these processes.

In the latter, there has been a tendency to convert crude oils into heavy oils, but the increased demand for lighter oils has disturbed the balance between supply and demand for petroleum products, so that currently the effective use of excess heavy oils is an important problem for the petroleum industry.

However, in the production of gas from olefins, such as ethylene, propylene, butadiene, etc., as well as monocyclic aromatics such as benzene, toluene, xylene, etc., light hydrocarbons, such as gases, are obtained in the oil extraction or in petroleum refinery products, such as naphtha mainly used. Prices rise because of the shortage of these light hydrocarbons, while the economic advantage of the gaseous olefins or monocyclic aromatics decreases considerably. In order to solve such a structural problem, various attempts have been made to prepare petrochemical starting materials by using lighter oils, such as kerosene, gas oil, vacuum gas oils, etc. asm. subjecting a hydrogenation treatment followed by steam pyrolysis. However, in these methods, different types of oils used are also available as petroleum products, so that the situation of the supply of starting material is in fact the same as for the light hydrocarbons, such as naphtha.

In both the petroleum industry and in the petrochemical industry, efforts are now being made to convert a heavy oil into a lighter and more valuable product, which can effectively be used as a light petroleum product or serves as a starting material for petroleum chemistry. Thus, a number of methods of hydrocracking or thermal cracking of heavy oils have been proposed, but none of these methods is satisfactory in the conversion of a heavy oil, such as a vacuum residue into a lighter product since they have all the drawbacks.

For example, in a fixed bed or fluidized bed hydrocracking method, wherein the reaction is carried out in a reactor packed with a granular or powdered catalyst, at a high conversion to lighter products, the catalyst is gradually poisoned by deposition of coal and metal components, that are present in the feed oil. This causes the activity of the catalyst to deteriorate or the catalyst layer to be clogged.

On the other hand, if a high conversion of a heavy hydrocarbon to a lighter product is to be carried out during thermal cracking, the so-called coking phenomenon will occur, which will lead to the process being stopped. Thus, this process is generally useful only when converted to a lighter product such that no coking problems occur. The so-called hydrovisbreak method has been proposed to improve this point. However, this method does not sufficiently counteract the coking effect even if the hydrogen pressure is increased to a high pressure of 300 kg / cm 2. A coking process has also been proposed, the conversion to lighter product being carried out while positively forming coke. In this process, a large amount of coke must be removed as an iron product, while the problem of low light oil yields persists. Furthermore, the obtained light oil is enriched in aromatic and olefinic components, as a result of which the quality deteriorates.

Thus, in the known methods, even if one wishes to convert a high-boiling material into a light production by catalytic processing of a heavy oil, the impurities present in the oil, such as sulfur or heavy metals, and Especially polymeric compounds significantly reduce the acidity of the catalyst. As a result, the problem arises that the cracking activity caused by the acidity of the catalyst does not persist.

Also, in thermal cracking of a hydrocarbon in the presence of a catalyst, the reaction rate appears to be faster the greater the molecular weight of the starting material. However, since the reaction rates of the side reactions such as coke formation and polycondensation are high, it is very difficult to increase the cracking rate in such reactions. *

Furthermore, various techniques have been reported for hydrotreating heavy hydrocarbons by reacting them in a dispersed state with the addition of solid materials.

U.S. Patents 3,131,142, 4,134,825, 4,172,814, and 4,285,804 describe hydrotreats in which an oil-soluble metal compound or an emulsion of an aqueous solution of a water-soluble metal compound is added. U.S. Patents 3,161,585 and 3,657,111 describe hydrotreats with a thermally cracked colloidal material of an oil-soluble metal compound or colloidal particles of vanadium sulfide. Canadian Pat. Nos. 1,073,389 and 1,076,983, U.S. Pat. Nos. 4,176,051, 4,214,977 and 4,376,695 describe hydrocracking using carbon powder or carbon powder coated with a metal salt. U.S. Patents 3,707,461 and 4,299,685 describe hydrotreating using coal ash. U.S. Pat. Nos. 4,169,038, 4,178,227 and 4,204,943, as well as Japanese Patent Publications 207688/1982 and 69289/1983 describe hydrotreats using coke by-product or petroleum as by-product. Japanese Patent Publications 40806/1979 and 141388/1981 describe hydrocracking using a desulfurized catalyst or a pulverized spent catalyst thereof. U.S. Patents 4,066,530 and 4,067,799 describe hydrotreating using combination of an oil-soluble metal compounds and iron component particles;

Japanese Patent Publication 108294/1983 describes hydrotreating using a combination of a metal compound and a metal-containing dust by-product, while U.S. Patents 3,331,769 and 4,376,037 describe such treatment using a combination of a metal compound and a porous solid catalyst or a porous support. Most of these techniques employ reaction conditions approximating desulfurization conditions, and they include proposals primarily aimed at metal removal, hetero atom removal, such as sulfur or nitrogen removal, or residual carbon removal from heavy hydrocarbons.

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-4- substances. Some of these techniques employ a heavy hydrocarbon, which is relatively easy to crack, attempting to achieve an appropriate degree of hydrocracking using a waste catalyst, coke by-product or a natural product. In either of these techniques, when used to decompose heavy hydrocarbons, such as an atmospheric residue or a vacuum residue in lighter products, the technical problems such as plant clogging or economic problems have not been solved.

10 Er. Extensive research has been conducted to overcome the drawbacks of the prior art and to develop a process which converts a heavy hydrocarbon feedstock economically and in high yields into a lighter and more valuable product. It has now been found that by adding at least two kinds of components, namely an oil-soluble or water-soluble transition metal compound and an ultra-fine powder with an average particle size in the range of 5-1000 ip and the thermal cracking in the presence of hydrogen gas or to carry out a hydrogen sulfide-containing hydrogen gas, suppressing side reactions of polycondensation and coke-20 formation, while also preventing coking in the plant, especially in reaction zones, so that stable valuable light oils are economically produced in high yield from a heavy hydrocarbon, while at the same time preventing deterioration of the residue.

More specifically, the present invention provides a method for converting a heavy hydrocarbon into a more valuable product, comprising:

Adding at least two kinds of materials to the heavy hydrocarbon, comprising an oil-soluble or water-soluble transition metal compound and an ultra-fine powder which can be suspended in a hydrocarbon and has an average particle size of 5-1000 µl; thermal cracking the heavy hydrocarbon in the presence of a hydrogen gas or a hydrogen sulfide-containing hydrogen gas; and recovering the resulting lighter hydrocarbon oil.

Figures 1 and 2 show flow charts for the various embodiments of the process for preparing gaseous olefins 840200? * 5-5 * and monocyclic aromatics, in which 3 a heater, 5 a high pressure gas-liquid separator, 8 an atmospheric evaporator, 10 a vacuum evaporator, 17 a liquid-solid separator, 20 a hydrotreating unit, 23 a high pressure gas-liquid separator, 26 is a gas-liquid separator and 29 is a steam pyrolysis unit.

The heavy hydrocarbon used in the present invention is a crude oil or an atmospheric residue or a vacuum residue of the crude oil, including slate oil, tar sands extracts and liquefied coal oil. A heavy hydrocarbon, which contains a large amount of a valuable fraction, which at a high conversion of the heavy oil into a lighter more valuable product, eg a fraction with a boiling point of 520 ° C or higher under atmospheric pressure, is economical favorable.

In the method of the invention for converting a heavy oil into a lighter, more valuable product, a sinergistic effect can be obtained by using at least two kinds of materials in combination. This is believed to be due to the operation to be described below.

It is believed to be an oil-soluble. or water-soluble transition metal compound by heat treatment in the presence of hydrogen and / or hydrogen sulfide in the reaction zone of a heavy hydrocarbon or in the preceding stage thereof is converted into a material which has a hydrotreated catalyst activity in a carbon, whereby polycondensation reactions or coke precursor or coke-forming reactions, which are unavoidable side reactions in the strong conversion of a heavy hydrocarbon to a lighter hydrocarbon, are suppressed. Other advantages are also obtained, such as suppressing the amount of gases formed as by-product, preventing deterioration. of the properties of the oil produced by the thermal cracking, etc.

Furthermore, it is believed that an ultrafine powder having the average particle size in the range of about 5-1000 µm which can be suspended in a hydrocarbon, the coking phenomenon in the reaction zone, which, also with the strong conversion of a heavy hydrocarbon into a lighter hydrocarbon is unavoidable, prevented by keeping the coke precursor, coke and the like in a floating state or by its ability to transport and migrate these materials. It is believed that when a transition metal compound is converted into a material having a hydrotreating catalytic activity it forms a high dispersibility and a high surface area. As a result, there are additional advantages, namely that the effect can already be achieved with a small amount of the transition metal compound and that it can be achieved even with a transition metal with a weak hydrogenation function.

In carrying out the process of the invention, wherein a heavy hydrocarbon is converted into a lighter more valuable product, it is essential that at least two kinds of materials, namely an oil-soluble or water-soluble transition metal compound or a material having a hydrotreating catalytic activity that can be converted from such a compound, as well as an ultrafine powder having an average particle size in the range of about 5-1000 µm are simultaneously present in a heavy hydrocarbon. However, it is not necessary to prepare a specifically formulated mixture in advance, it is sufficient to add these materials separately to a heavy hydrocarbon feedstock.

Even when the resp. components are added separately, the transition metal compound will interact with the ultrafine powder, completely converting it into the system, which exhibits the desired effect in the reaction zone or in the stage before the reaction zone. The ultra-fine powder must be suspended in a heavy hydrocarbon. By suspended here is meant the state in which the solid particles are mainly present in a liquid or the state in which the solid phases are distributed discontinuously by the liquid phase, which is a continuous phase, including colloidal, slurry or pasta state.

It is of course also possible to prepare a material system with the desired function in advance and to add this system to the heavy hydrocarbon. E.g. an oil-soluble transition metal compound is dissolved or an aqueous solution of a water-soluble transition metal compound is emulsified in an oil, such as a gas oil or vacuum gas oil, while an ultrafine powder having an average particle size in the range of about 5-1000 µm in the solution or emulsion is dispersed. The resulting dispersion is heat-treated at a temperature at which the transition metal compound is decomposed in the presence of hydrogen gas or a hydrogen sulfide-containing hydrogen gas to prepare a solid, which is separated or concentrated by a known solid-liquid separation method, and. then added to a heavy hydrocarbon. The heavy hydrocarbon is then used in the process of the invention in the presence of hydrogen gas or a hydrogen sulfide-containing hydrogen gas. As another example, a gaseous phase of hydrogen gas or hydrogen sulfide-containing hydrogen gas with an ultra-fine powder having an average particle size of about 5-1000 ny distributed therein is heated and an oil solution consisting of an oil-soluble transition metal compound is dissolved in the oil or a water solution with a water-soluble transition metal compound dissolved in water injected into its atmosphere to decompose the transition metal compound, followed by drying. The solid obtained is added to a heavy hydrocarbon oil, which is then subjected to the thermal cracking according to the invention. However, in the impregnation method or the precipitation method in which the transition metal compound is supported on an ultra-20 fine powder, it is not desirable to use a preparation method involving agglomeration or sintering between reciprocal transition metal compounds, between reciprocal ultra-fine powders or between the transition metal compound and the ultra-fine powder may occur.

Another material system with the desired properties is available by a thermally cracked product obtained according to the process of the invention or a heavy residue which has been fractionated by distillation of the thermally cracked product as such or optionally to use a solid separated and recovered from these dispersed oils.

In the oil-soluble or water-soluble transition metal compound, the transition metal includes all transition elements in the Periodic Table of the Elements, and in particular vanadium, chromium, iron, cobalt, nickel, copper, molybdenum, tungsten and mixtures thereof.

Examples of the oil-soluble compounds containing the desired transition metals are the so-called pi complexes, which contain the 8402008-8-cyclopentadienyl group or the allyl group as the ligand, organic carboxylic acid compounds, organic alkoxy compounds, diketone compounds, such as acetylacetonate complex carbonyl compounds, organic sulfonic acid or sulfinic acid compounds, xanthic acid compounds such as dithiocarbamate, amine compounds such as organic diamine complexes, phthalocyanine complexes, nitrile or isonitrile compounds, phosphine compounds and others. Particularly preferred as oil-soluble compounds are salts of aliphatic carboxylic acids, such as stearic acid and the like, since they have a high solubility in the oil, do not contain a heteroatom such as nitrogen or sulfur and can be converted relatively easily into a material with a hydrotreating catalytic activity . Preferred are compounds of smaller molecular weights, since small amounts thereof can be used to provide the necessary amount of the transition metal.

Examples of water-soluble compounds are cafbonates, carboxylates, sulfates, nitrates, hydroxides, halides and ammonium or alkali metal salts of transition metal acids, such as ammonium heptamolybdenate.

An oil-soluble transition metal compound can be used as the solution, which can be added directly to the heavy hydrocarbon. However, in a water-soluble transition metal compound, it is necessary to form an emulsion by adding a water solution thereof to the feedstock of a heavy hydrocarbon. Here, any known emulsification method, including the use of the emulsifier, is flexible.

The ultra-fine powder with an average particle size of about 5-1000 µm, which can be suspended in a hydrocarbon, has an excellent effect compared to solid catalysts, 30 carriers used for solid catalysts and powdered products thereof, such as those in the known in the art.

I.e. (1) it has a high dispersibility and moves freely in the reaction zone, creating places for uniform reactions without inhomogeneities? (2) it will remain in reaction zone 35 only briefly, but poly-condensed products, such as asphaltenes, coke precursors, coke, etc., attached or deposited thereon in highly dispersed, flowing 84 02 0 0 8 β-9-9 easily remove the condition from the reaction zone, preventing blockage? and (3) it will prevent agglomeration of materials having a hydrotreating catalytic activity formed from the transition metal compound by a strong S dispersion thereof, thereby greatly increasing the activity of the material having the hydrotreating catalytic activity.

However, the main property of the ultrafine powder is an extremely large external specific surface area, compared to porous solid catalysts and supports. The known solid catalysts and supports, even when crushed, will have a general particle distribution ranging from several micrometers to several tens of micrometers, with a very small external surface area. The expected effect is mainly due to the internal surfaces within the pores. However, in the case where the reaction takes place within the pores, the diffusion rate of the reactants becomes a problem and a concentration gradient of the reactants arises between the central part of the particle and the proximity of the surface, making the reaction site inhomogeneous . Sufficient effect is hereby not obtained, while the physical structure, such as the pore distribution or the particle distribution of the pulverized materials, can also have a strong influence on the obtained effectiveness. Furthermore, when using heavy hydrocarbons, high molecular weight materials therein, such as asphaltenes, porphyrin-like materials containing heavy metals and coke precursors or formed coke, will not penetrate the interior parts of the pores, but will rapidly clog pores in the vicinity of the surface, which prevents the internal surfaces from functioning properly. In contrast, the ultra-fine powder is a material system, which is virtually non-porous and will not become porous and which, due to the effect of only the large outer surface, beneficial effect. The outer surface is greatly enlarged as the particle sizes become smaller. For example, with particle size of 10-50 my, the specific surface area can be about 300-60 m / g, which gives a particularly good effect. The ultrafine powders meeting these conditions can be divided into inorganic and carbonaceous substances. Examples of inorganic substances are 8402008

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lead so-called fine refractory particles, such as ultra-fine finely divided silica, silicates, alumina, titania, etc., and ultra-fine metal particles, such as those obtained by vapor deposition. Ultrafine particles of silicic acid and silicates comprise a group of 5 materials, commonly referred to as white carbon, which can be synthesized by vapor phase methods, such as by thermal decomposition of silicon halides, thermal decomposition of silicic acid-containing compounds, thermal decomposition of organic silica compounds etc .; and also by liquid phase methods, such as decomposing sodium silicate with an acid, decomposing sodium silicate with an ammonium salt or alkali metal salt, forming an alkaline earth metal silicate from sodium silicate, followed by decomposition with an acid, ion exchange through an aqueous sodium silicate solution treatment with an ion exchanger-resin, decomposition under pressure of an organogel, decomposition of silicon halide with water, decomposition of sodium silicate solution with silicic acid, which is a by-product in the preparation step of calcium superphosphate, the preparation using natural silicic acid or silicates, the reaction of sodium silicate with hydroxide, such as calcium hydroxide or calcium chloride, aluminum chloride or sodium aluminate, the treatment of quartz or silica gel with calcium hydroxide in an autoclave, etc. The particle size can be measured by an electron microscope and varies approximately 5 -50 my although somewhat dependent on the type of material. As for the specific surface area, the external specific surface area is calculated from the particle size measured by an electron microscope, the specific surface area determined by the gas adsorption method (BET method) essentially coinciding with it, which is in the range of approximately 50 -400 m / g.

30. The carbonaceous materials, on the other hand, are a group of materials obtained through carbon formation, namely carbonization, which can be divided into liquid phase or solid phase carbonized materials such as petroleum coke, coke, pitch coke, activated charcoal, charcoal, etc. and gas phase carbonized materials, such as carbon blacks. Carbonaceous materials are flammable compared to inorganic materials and therefore advantageous when 8402008 -11-ml becomes the heavy residue, which is a product remaining after the conversion reaction of a heavy hydrocarbon into a lighter more valuable hydrocarbon, as boiler fuel applied.

The liquid phase or solid phase carbonized materials 5 generally have large particle sizes and most of them must be pulverized and sieved to achieve the desired particle size. On the other hand, most gas phase carbonized materials have particle sizes that fall in the range desired according to the invention, making them readily available as such. Of these, carbon blacks include various options, which can be prepared by, for example, the oil furnace method, gas furnace method, duct method, thermal method, acetylene carbon black method, carbon black method, lamp black method, etc. The particle size is measured by an electron microscope and is approximate 9-500 µm, although for some species 9-100 µm, except for the products obtained by the thermal method. As for the specific surface area, the specific outer surface area, calculated from the particle size obtained with the electron microscope and the specific surface area, determined by the gas adsorption method, are almost equal to each other and are in the range of approximately 5-400 m / g.

When the ultrafine powder of the present invention is added to a heavy hydrocarbon feed, it can be added directly as such or as a concentrated dispersion in another medium. The dispersion, which contains an ultra-fine powder, can be mechanically processed, eg by a stirrer, ultrasonic waves or in a mill, or optionally or in combination with dispersants, such as a neutral or basic phosphonate, a metal salt, such as a sulfonic acid salt calcium or barium, succinimide and succinate, benzylamine or a polypolar type polymer compound.

In carrying out the method according to the invention, the amounts of two types of material to be added are in the range of 10-1000 ppm, most preferably 50-500 ppm, for the transition metal compound, calculated as the metal, based on the weight of the heavy hydrocarbon feed and in the range of 0.05-10 wt%, most preferably 0.1-3 wt% for the ultrafine powder on the same weight basis. When preparing a material system to which 8402008 is.

In order to provide the desired function, a mixture will be prepared in amounts of the two. components,. that fall within the above-mentioned areas. At less than 10 ppm of the transition metal of the transition metal compound, based on the heavy hydrocarbon, or at a level of less than 0.05 wt.% Of the ultrafine powder, a sufficient effect is not obtained in suppressing the side reactions of the polycondensation reaction and the coking, while also the coking cannot be sufficiently prevented. If more than 1000 ppm of transition metal of the transition metal compound is used, or more than 10% by weight of the ultrafine powder, no further improvement corresponding to such amounts is obtained, but rather unfavorable side reactions or a solid-liquid separation in the reaction zone are obtained. with accompanying blockages.

In carrying out the process according to the invention, the thermal cracking conditions depend on the heavy hydrocarbon material used and the properties and amounts, of the two materials added, generally the reaction temperature will be in the range of 400 -550 ° C, and preferably is 430-520 ° C. At higher temperatures, thermal cracking will continue to produce significant coke and gas formation until there is virtually no feed material that can be converted to the lighter oil. If the temperature is lower than the stated range, the thermal cracking rate will be very low.

The reaction pressure is usually 30-300 kg / cm, and preferably 50-250 kg / cm2.

The thermal cracking can be either batch or continuous, with the reaction time or residence time of the heavy hydrocarbon in the reactor being 1 minute to 2 hours, usually 3 minutes 30 to 1 hour. These processing conditions are interdependent, so that the optimal trajectory will depend on the situation. The amount of hydrogen fed in practical thermal cracking can be 100-5000 Nm ^ / kl and most preferably is 500-2000 Nm ^ / kl, expressed in volume ratio to the feedstock, with it being it is generally desirable to supply hydrogen gas during the process in an amount corresponding to the amount of hydrogen gas consumed. Very pure hydrogen gas or a gas mixture containing a large amount of hydrogen gas can be used. When using hydrogen sulfide-containing hydrogen gas, the amount used will correspond to that mentioned above for the total amount, the content of hydrogen sulfide being preferably 1-10 mol%.

The continuous run reaction plant may be a tubular reactor, a tower reactor or a heating vessel reactor, in which it is desirable in all cases to conduct reaction and slurry, maintaining the ultrafine powder in a suspended state without forming a fixed bed, fluidized bed. or boiling bed.

The reactor structure can be simpler for a slurry reaction, while the reaction temperature can be more easily adjusted without the capacity deteriorating over time or coking clogging. A short, high temperature reaction can be carried out relatively easily at a high space velocity, thereby obtaining a large capacity per unit, with the additional advantage that the amount of hydrogen gas consumed becomes smaller while suppressing any hydrogenation activity, such as hydrogenation of aromatic rings.

Of the resulting product oils, the distillates can be used as a naphtha substitute in petroleum chemistry as a whole or after fractionation, or they can be separated into fractions with resp. cooking ranges for use as intermediate materials for petroleum products such as gasoline, jet fuel oil, kerosene, gas oil, diesel fuel, lubricant and others.

In the method of further hydrotreating the hydrocarbon oil, which has been obtained as the lighter, more valuable product of the method of the invention, the hydrocarbon oil as such or after removal of its high boiling fraction may be hydrotreated be subjected. The hydrotreating is preferably carried out after the high boiling fraction has been removed, since it also removes substances such as asphaltenes or metals. The high boiling fraction removed by the separation can further be treated in much the same way as liquid fuel oil, which can be used as the fuel source in the process of the invention or otherwise for use in boilers. For the separation of the high boiling fraction, conventional methods can be used, such as higher pressure gas separation, atmospheric distillation, vacuum distillation and further solvent deasphalting.

The catalyst 5 to be used in the hydrotreating process can be any catalyst used for hydrotreating petroleum fractions and heavy oils, in particular a catalyst containing at least one type of metal selected from Group VIb metals and the group VlII Metals of the Periodic System, such as metal combinations of nickel-molybdenum, cobalt-moybdenum, nickel-tungsten, and the like, supported on an inorganic porous support. These metal combinations are usually used as oxides or sulfides, the inorganic porous. carrier, e.g., alumina, silica, silica-alumina, zeolite, zeolite-containing alumina, alumina-boria, silica-alumina-titania and others. The hydrotreating conditions are selected as desired, depending on the feedstock heavy hydrocarbon oil and the properties of the catalyst, the reaction temperature being 250-480 ° C, and preferably 300-45 ° C. If the reaction temperature is higher than 480 ° C, the thermal cracking of the side reaction goes too fast, as a result of which more carbon is deposited on the catalyst, the amount of hydrogen used increases with an increased gas formation and further reduction of the liquid reaction.

yield occurs. When, on the other hand, the temperature is below 250 ° C

2, the reaction rate becomes too slow. The reaction pressure can be 3-300 kg / cm 2 and is preferably 50-250 kg / cm, which is highly dependent on the hydrotreating capacity of the catalyst. The liquid space velocity per hour (LHSVj can be 0.1-5.0 hours, and is preferably 0.2-3.0 hours *, while the amount of hydrogen to be fed is in the range of 200-2000 Nm'Vkl expressed as the volume ratio to the feed oil subjected to the hydrotreating These conditions are interdependent so that optimal ranges depend on the requirements set, including, of course, the properties of the feed oil and the catalyst activity, as well as the application purpose of the hydrotreated product oil.

The process for the preparation of gaseous olefins and mono-35 cyclic aromatic hydrocarbons using a heavy hydrocarbon as feedstock comprises the first embodiment:.

8402008 t -15- (A) adding a heavy hydrocarbon (i) at least two kinds of materials comprising an oil-soluble or water-soluble transition metal compound and an ultra-fine powder suspended in a hydrocarbon and having an average particle size in the range from 5-1000 m2; or (ii) a solid prepared by dissolving an oil-soluble transition metal compound in an oil or emulsifying an aqueous solution of a water-soluble transition metal compound in an oil; dispersing an ultra-fine powder having an average particle size in the range of 5-1QQQmy in the oil solution or in the oil / aqueous emulsion; and heating the dispersion to a decomposition temperature of the transition metal compound in the presence of a hydrogen gas or a hydrogen sulfide-containing hydrogen gas; or (iii) a solid prepared by dissolving an oil-soluble transition metal compound in an oil or dissolving a water-soluble transition metal compound in water and converting the solution to a dry solid by dissolving the solution in spray a hydrogen gas or a hydrogen sulfide-containing hydrogen gas, in which ultrafine powder having an average particle size in the range of 5-1000 µm dispersed is present, and simultaneously heating the gas to decompose the transition metal compound and dissolve the solid to dry; B) thermal cracking of the heavy hydrocarbon in the presence of a hydrogen gas or a hydrogen sulfide-containing hydrogen gas and recovery of the resulting lighter hydrocarbon oil; C) removing a high boiling fraction from the lighter hydrocarbon oil; and D) pyrolyzing a low boiling fraction or a mixture of the fraction and a petroleum fraction with steam, and recovering a gaseous olefin product and a monocyclic aromatic product.

Optionally, the method comprises according to a second embodiment; A) adding to a heavy hydrocarbon (i) at least two kinds of materials, comprising an oil-soluble or water-soluble transition metal compound and an ultra-fine powder suspended in a hydrocarbon and an average particle size in the range of 5-1000 my has; or (ii) a solid prepared by dissolving an oil-soluble transition metal compound in an oil or emulsifying an aqueous solution of a water-soluble transition metal compound in an oil dispersing ultra-fine particles with an average particle size in the range of 5-1000 µm in the oil solution or in the oil / water emulsion; and converting the dispersion to a solid by heating the dispersion at the decomposition temperature of the transition metal compound in the presence of a hydrogen gas or a hydrogen sulfide-containing hydrogen gas; or (iii) a solid prepared by dissolving an oil-soluble transition metal compound in an oil or dissolving a water-soluble transition metal compound in water; and converting the solution to a dry matter by spraying the solution into the hydrogen gas or a hydrogen sulfide-containing hydrogen gas, in which ultrafine particles having an average particle size in the range of 5-1000 µm are dispersed, and simultaneously spraying the gas heating to decompose the transition metal compound and dry the solid; B) thermally cracking the heavy hydrocarbon in the presence of a hydrogen gas or a hydrogen sulfide-containing hydrogen gas and recovering the resulting lighter hydrocarbon oil; C) removing a high boiling fraction from the lighter hydrocarbon oil; D) hydrotreating a low boiling point fraction under hydrogenation conditions and recovering the resulting hydrotreated oil; and E) pyrolyzing the hydrotreated oil or a mixture of the hydrotreated oil and a petroleum fraction with steam and recovering a gaseous olefin product and a monocyclic aromatic product.

According to a third embodiment of the method, in the method according to the first and second embodiments, as defined above, all or part of the solid which is separated from the lighter hydrocarbon oil obtained in step B) is recovered or the stage C) removed high boiling fraction returned to stage B).

According to a fourth embodiment of the method, in the method according to the first or second embodiment as defined above in step C), removed high-boiling fraction is returned in whole or in part to step B).

8402008 -17-

Thus, the method of preparing gaseous olefins and monocyclic aromatics of the present invention comprises four or five basic steps. The four-step process consists of a step of adding at least two kinds of materials to a heavy hydrocarbon, the thermal cracking step, the step of removing a high boiling fraction and the steam pyrolysis step. In the five step process, there is the hydrotreating step between the high boiling fraction removal step and the steam pyrolysis step.

In the thermal cracking step, the heavy hydrocarbon is converted into a lighter, more valuable product. By effecting the addition of at least two kinds of materials to a heavy hydrocarbon feedstock in the presence of hydrogen gas or hydrogen sulfide-containing hydrogen gas, the side reactions of polycondensation and coke formation can be prevented, including coking in an installation especially in the reaction zone can be prevented, so that a useful stable lighter oil can be obtained economically in high yield from a heavy hydrocarbon, with the additional advantage that the deterioration of the properties of the lighter oil as well as the high boiling residue can be prevented. This can be particularly demonstrated in the case of using an atmospheric residue or a vacuum residue of a paraffin-based crude, such as Minus crude, Taching crude, etc., which are known as particularly heavy oil.

More specifically, it was believed that these heavy residues are difficult to convert into lighter valuable products due to phase separation of the product. According to the present invention, it has become possible to achieve a strong conversion to a lighter, more valuable product by using the excellent paraffinic properties of these heavy oils. Thus, the low boiling fraction of the lighter product obtained by atmospheric vacuum distillation can be used directly in the steam pyrolysis without further subjection to the hydrotreating step to provide petroleum chemistry starting materials. As a result, installations such as hydrotreating columns are no longer necessary, while also less hydrogen 8402008 / -18- is consumed. Furthermore, the high boiling residue can. removed by distillation, are used as liquid fuel in much the same way as the direct heavy oils as a fuel source in the practice of the present process or generally for boilers.

The removal of a high boiling fraction is necessary to add a low boiling fraction to the subsequent steam pyrolysis or hydrotreating steps. To remove. a high boiling fraction, high pressure gas separation, atmospheric distillation or vacuum distillation can be used, as well as further solvent deasphalting. It is also possible to carry out fractionation in naphtha fractions (boiling point below 200 ° C), kerosene gas oil fractions (boiling range 200-340 ° C) and vacuum gas oil fractions (boiling range 343-445 ° C). Different kinds of these lighter fractions can be subjected to steam pyrolysis as such or after hydrotreating.

When subjecting the thermally cracked oil to the hydrotreating step after removing the high-boiling fraction, the hydrotreating method as described above can be used as such. However, since the starting oil used is the thermally cracked oil from which the poison catalyst materials such as asphaltenes and metals have been removed, the catalyst used has greater activity at a greater specific surface area of the porous support, so that it is not particularly necessary. increase pore volume or use large pore sizes, such as in the catalyst for treating an oil with a high content of asphaltenes or metals.

The thermally cracked oil from which the high-boiling fraction has been separated and removed or the hydrotreated oil obtained from the hydrotreating step can be used as feed oil in the steam pyrolysis step 30 and it is also possible to use the steam pyrolysis of each fraction fraction separately or as a mixture with other petroleum fractions depending on the purpose.

The steam pyrolysis used in the invention is not particularly critical, but various embodiments can be used, and it is also possible to use a tubular heater which is an existing naphtha cracking heating unit or to modify it somewhat.

8402008 -19-

The reaction conditions in the steam pyrolysis step include a steam oil weight ratio of 0.2 to 2.0, preferably 0.4 to 1.5, a pyrolysis temperature of 700-900 ° C, preferably 750-900 ° C and a residence time of 0.05 -2.0 seconds, preferably 0.1-0.6 seconds.

The product obtained by the steam pyrolysis reaction is led from the heater to a rapid cooling heat exchanger, where the heat is recovered, after which gaseous olefins and monocyclic aromatics are obtained after separation and purification, as well as fuel oils as a by-product and also hydrogen and hydrocarbons as a by-product .

In the practice of the process of the invention, the hydrogen gas used in the thermal cracking step and in the hydrotreating step can be supplied by circulation of the hydrogen gas, which flows from the resp. steps has been separated, sometimes after the hydrogen sulfide and ammonia present therein have been removed, it being generally desirable to supply hydrogen gas in an amount corresponding to the amount of hydrogen gas used. As hydrogen source, the hydrogen gas by-product in the steam pyrolysis or the hydrogen gas obtained in the steam modification of the hydrocarbon by-product gas or the by-product steam oil can also be used as such.

The drawings describe the process for preparing gaseous olefins and monocyclic aromatics using a heavy hydrocarbon oil as feedstock, but the invention is not limited thereto.

Figures 1 and 2 show various examples of flow charts for carrying out the process for preparing gaseous olefins and monocyclic aromatics of the present invention.

In Figure 1, the feed material, consisting of a heavy hydrocarbon oil mixed with at least two kinds of material according to the invention, is pressurized by means of a feed pump and introduced through a conduit 1, the pressure of the hydrogen gas or hydrogen sulfide -containing gas is supplied by means of a compressor, which gas is supplied via a pipe 2 in a thermal cracking plant 3, in which the heavy hydrocarbon is converted into a lighter, more valuable product. The lighter product obtained is delivered via a line 4 to a gas-liquid separator 5, in which it is cooled rapidly. The high pressure gas-liquid separator generally consists of the two stages of a hot and cold separator. The hydrogen-enriched gas from the separator is discharged via a pipe 6 and, if desired, after increased to a desired pressure, is led to the thermal cracking installation 3. The liquids from the hot separator and the cold separator do not need to be preheated and pass through a pipe 7 to an atmospheric evaporator 8.

The atmospheric residue passing through a discharge pipe 9 from the bottom of the atmospheric evaporator. 8, then proceeds to a vacuum evaporator 10 in which it is treated. The vacuum evaporator 10 is brought under vacuum by a vacuum-drawing device for the purpose of lowering the operating temperature, and it is sometimes also possible to use steam distillation as an aid, whereby steam is blown from the bottom of the tower, in order to reduce the partial pressure of lower the oil. The atmospheric fraction from the atmospheric evaporator 8 and the vacuum fraction from the vacuum evaporator 10 are mixed after removal of the waste gases via the pipes 11 and 12, passing them via pipes 13 and 14 in pipe 15. The vacuum residue, which is discharged from the bottom of the vacuum evaporator 10 via a discharge pipe 16, on the other hand, can be used as such as a liquid fuel, but it can also be fed into a solid separator 17, where it is subjected to a separation step. . The solid-state separator 17 may comprise, for example, a centrifugal separator, a filter, a solvent, a settling tank and a combination thereof. Some of the vacuum residue or solid or solid that has been subjected to further cleaning and drying steps (not shown) can be recycled via line 18 to the heavy hydrocarbon feed. The liquid vacuum residue isolated from the solid in the solid separator 17 is discharged through line 19 and can be used as a liquid fuel. The distillate oil introduced into the line 15 is pressurized by a feed pump and fed into a hydrotreater 20 in which it is hydrotreated with hydrogen gas pressurized by a compressor.

The hydrotreated product is cooled to the desired temperature by a heat exchanger, etc., and discharged through a conduit 22 to a high pressure gas-liquid separator 23, where it is separated into gas and liquid. The separated hydrogen-enriched gas is returned via a line 24, if necessary after elevation to a desired pressure, to the hydrotreating plant 20. The hydrotreated product itself is depressurized by passing through a line 25 and leading to a gas-liquid separator, after which after discharge of the waste gas with high vapor pressure via line 27, it is fed via line 28 to a steam pyrolysis installation 29. In this plant, the hydrotreated product is then pyrolyzed and the pyrolized product is discharged through line 30, cooled, separated, purified and recovered in the form of gaseous olefins, monocyclic aromatics, hydrogen by-products, fuel oil by-products, etc.

The flow chart of Figure 2 shows the case that no hydrotreating step is needed and corresponds to the portion of Figure 1 in which symbols 20 and 28 are omitted.

The present invention is further described in detail by the following examples, to which, however, the invention is not limited.

Example I

The thermal cracking was performed using the continuous type installation operating at high pressures in a vacuum using Minus crude oil (100 wt% of a fraction boiling above 520 ° C) as feed oil. reactor of a heatable type vessel comprising an inner diameter of 40 mm and a height of 100 mm, equipped with a stirrer, provided with three turbine-like blades, each with three blades. The two components to be fed to the feed oil consisted of nickel octoate in an amount of 200 ppm nickel, based on the feed oil and furnace soot (average particle size 20 ny by electron microscopy (EM), specific surface area 120 m? / G by BET method) in an amount of 2% by weight, based on the feed oil, the feed oil being thoroughly stirred before it was fed into the reactor.

The reaction conditions ö 0 used for the thermal cracking were a temperature of 495 ° C, a pressure of 200 kg / cm, a residence time (based on cold liquid) of 20 min and a hydrogen / feed oil ratio of 2000 Nl / l, where the number of revolutions 8402008 -22-

J

It was less than 1000 rpm. The continuous probation period was 100 hours calculated as the stationary probation period.

The products obtained were 5.8 wt% C 2 -C 4 gases, 45.2 wt% of the GO fraction by atmospheric distillation (bp 343 ° C)), 29.0 wt% of the VGO fraction by vacuum distillation (bp 343-520 ° C) and 20.0 wt% of the vacuum residue (VR). The asphaltene content (defined as insoluble in hexane and soluble in tetrahydrofuran) was 2.1 wt% and the amount of coke (defined as insoluble in both tetrahydrofuran and hexane) was 1.0 wt%. The amount of hydrogen used was 110 N / l per kg of the feed. The conversion of the heavy feed materials into the lighter, more valuable product as defined by the following formula: / Fraction amount with a boiling point higher than \ 1,. a boiling point higher than 520 ° C in feed / was found to be 80% by weight. The yield of the liquid fraction converted to a lighter product with a boiling point below 520 ° C was 74.2% by weight as the sum of GO and VGO.

Furthermore, the measure of coking (deposit amount) 20 on the interior wall surface of the reactor after 100 hours of stationary operation was found to be exceptionally small, namely 40 ppm, based on the total weight of the oil supplied.

Comparative example 1

Example X was repeated, except that the two kinds of components were not added to the feed oil. Two hours after the start of the test, the reactor was completely clogged with coke, while the test could no longer be run stably. Under conditions permitting stable operation, the yield of the liquid fraction having a boiling point below 520 ° C was 34.1 wt%, which is less than half the yield of Example I.

Comparative example 2

Example I was repeated with the exception that no ultrafine particles were supplied, but only nickel octoate in an amount of 500 ppm, calculated as nickel. Four hours after the start of run 35, the reactor had completely stopped with coke. The yield of the liquid fraction having a boiling point below 520 ° C was 75% by weight, but the amount of coke formed was 3.5% by weight and the majority thereof, namely about 3.0% by weight. was found to participate in the coking in the reactor.

Comparative Example 35 Example I was repeated except that no transition metal compound was added and only furnace carbon black was used in an amount of 4% by weight. 15 hours after the start of the test, the reactor was completely clogged with coke. The yield of the liquid fraction having a boiling point below 520 ° C was 74% by weight, but the amount of coke formed was high, namely 6.1% by weight, the amount of coking in the reactor being about 0.8 wt%.

Comparative example 4

Example I was repeated except that 3 wt% of pulverized delayed coke adjusted to a particle size distribution in the range of about 10-60 µ was used in place of carbon black.

3 hours after the start of the test, the reactor was completely clogged with coke. The yield of the liquid fraction having a boiling point below 520 ° C was 73 wt%, but the amount of coke formed was 3.1 wt%, with about 2.2 wt% found to be co-co-co-ested with 20 in the reactor added pulverized delayed coke.

Comparative example 5

Example I was repeated except that 3 wt.% Of a nickel-tungsten H catalyst supported on porous Y-alumina with a specific surface area of 220 m / g (BET method) containing 4 wt.% Nickel-oxide and 5 wt% tungsten oxide, and was pulverized to particle sizes of 60 y or less, instead of nickel octoate and carbon black was used. After about 7 hours of operation, the reactor was completely clogged and the test could no longer be continued. The liquid fraction of the oiling fraction having a boiling point below 520 ° C was 72 wt.%, The amount of coke formed being 1.8 wt.%, But within the reactor about 1.2 wt.% Coke was found to be coke-coated in the form, which partly contained added catalyst.

Comparative example 6

Example I was repeated except that an aqueous solution of ammonium molybdenate dissolved in water at 500 ppm was added as molybdenum in the feed oil to form 8402008 g -24-

V

of an emulsion, further comprising 3% by weight of pulverized particles with a size of about 10-30 µm of a complex oxide of silica-alumina (silica 60%, alumina 40%), which was a porous material with a specific surface of 400 m / g (BET method) instead of nickel-5 octoate and carbon black were added. After a test period of about 10 hours, the reactor was completely clogged and it was no longer possible to continue the test. The yield of the liquid fraction having a boiling point below 520 ° C was 75 wt% and the amount of coke formed was 3.5 wt%, but within the reactor about 1.2 wt% of the coke was found to have coking in the form which partly contained the added finely divided material.

As is evident from the results of Example I and Comparative Examples 1-6, the present invention gives excellent results in high yield of a lighter oil by cracking a heavy hydrocarbon. In addition, the residual oil has a boiling point higher than 520 ° C, which is obtained by the present process, a viscosity of not more than 22 est at 150 ° C, and the flammability, according to thermogravimetallic analysis, is equal to that of the vacuum residue of the supplied Minus crude oil, which is suitable as fuel oil.

Examples II-X

Using a vacuum residue of Minus crude oil (100 wt% of the fraction has a boiling point higher than 520 ° C) as the feed oil, various combinations of the two kinds of components in predetermined amounts as mentioned below were added, with the thermal cracking was carried out in the same reaction equipment as in Example I.

That is, in Example II, vanadium octoate was added in an amount of 300 ppm as vanadium and channel carbon black (average particle size 14 ny (EM method), surface area 300 m / g (BET method)) in an amount of 2 wt% .

In the case of Example III, copper octoate was added in an amount of 500 ppm as copper and silica products made by a liquid phase process (average particle size 20 µm.

35 (E.M. method), specific surface area 150 m ^ / g (BET method)) were added in an amount of 2% by weight.

8 4 ü 2 0 0.8 t -25-

In Example IV, molybdenum naphthenate was added in an amount of 100 ppm as molybdenum and silica products were obtained by vapor phase methods (average particle size 8 mu (EM-2 method), specific surface area: 350 m / g (BET method)) in an amount 5 of 1 wt% added.

In Example V, an aqueous solution of ammonium hepta-tungstate in an amount of 600 ppm was added as tungsten, while alumina, obtained by a vapor phase process (average particle size: 20 µm (EM method), specific surface area: 100 mVg (BET method) )) in an amount of 3% by weight was added.

In Example VI, an aqueous solution of cobalt sulfate was added in an amount of 800 ppm as cobalt and an anatase-type titanium oxide was obtained by a vapor phase process (average particle size: 30 ny (EM method), specific surface area: 15 50 rn ^ / g (BET method)) in an amount of 6% by weight.

In Example VII, nickel stearate was added in an amount of 300 ppm as nickel and calcined coke pulverized by a jet (average particle size 400 ny (EM method), specific surface area: 35 m ^ / g (BET method)) in an amount of 10 wt% added.

In Example VIII, chromium resinate was added in an amount of 700 ppm as chromium and thermal decomposition carbon black (average particle size: 180 πη * (EM method), specific surface area 35 n? / Q (BET method)) was added in an amount of 7 wt% .

In Example IX, nickel acetylacetonate was added in an amount of 500 ppm as the nickel and flowing coke pulverized by a jet (average particle size: 800 my (EM method), specific surface area: 25 m ^ / g (BET method)) in an amount of 10% by weight added.

In Example X, iron pentacarbonyl was added in an amount of 100 ppm as iron, while, silicate produced by a liquid phase process (containing 18% calcium oxide) [average particle size: 30 µm. (E.M. method), specific surface area: 80 m / g (BET method)] in an amount of 3% by weight was added.

In Examples VII and IX, further 1 wt.% Of a dispersant, composed essentially of calcium petroleum sulfonate and a 8402008 t -26 dispersant, composed of polybutenylsuccinimide was further added to feed oil.

The thermal cracking reaction conditions were a temperature of 495 ° C, a pressure of 200 kg / cm 2, a residence time (based on cold liquid) of 20 minutes and the stirrer speed of 1000 rpm in all examples. II-X, a hydrogen / feed oil ratio of 2000 Nl / 1 in examples It-VII, as well as hydrogen with 3 mol% hydrogen sulfide / feed oil ratio of 2000 Nl / 1 in examples VIII-X. The stationary operating state for each example lasted 30 hours.

In all these examples, a stable operation was possible without clogging the reactor, the conversion being in the range of 75-85% by weight and the yield of the liquid fraction having a boiling point of less than 520 ° C in the range of 70-85% by weight. 78 wt% was. Also, the amount of coke formed was in the range of 0.7-2 wt%, while the amount of coking on the surface of the inner wall in the reactor was in the range of 40-200 ppm based on the total weight of the feed oil.

Example XI

20 An Arabian light vacuum gas oil (bp 343-520 ° C), which is 1000 ppm, calculated as nickel, nickel stearate and 10% by weight of furnace carbon (average particle size: 15 mu (EM method), specific surface area 200 m / g) was loaded in an amount of 3 kg into an autoclave with an internal volume of 10 liters, hydrogen gas containing 5 mol% hydrogen sulfide was pressurized in the autoclave 2 at an input pressure of 100 kg / cm, after which the reaction with stirring at 1000 rpm at a temperature of 420 ° C for one hour. After the reaction, the contents were filtered, washed and extracted with tetrahydrofuran, followed by drying to a solid product. The solid product was added a vacuum residue of Minus crude oil, dissolved by heating (100% by weight of the fraction boiling above 520 ° C) to a content of 10% by weight and dispersed therein by ultrasonic waves. The resulting dispersion was added to the same Minus vacuum residue as mentioned above to a solids content of 2% by weight. The mixture was stirred thoroughly and used in the stationary run of the reaction in the same reactor and under the same reaction conditions as in Example 1 for 30 hours.

The experiment showed that the run could be continued stably without clogging the reactor, the conversion being 81.6 wt% and the yield of the resulting liquid fraction having a boiling point below 520 ° C 75.6 wt. % used to be. The amount of coke formed was 0.8 wt% and the amount of caking on the surface of the inner wall of the reactor was 40 ppm based on the total weight of the feed fed.

Example XII

Silica products were prepared by a vapor phase process (average particle size: 16 mu (EM method), specific surface area 2 200 m / g (BET method}}. 300 g of which was suspended in a fluidized bed in hydrogen gas containing 5 mol% hydrogen sulfide. and contacted with a sprayed mixture of a water solution of ammonium heptamolybdate in an amount of 15 g as molybdenum while moving through the gas stream, then the reaction was carried out for one hour while maintaining the temperature of the gas stream at 430 ° C. solid product obtained by this procedure was added to the vacuum residue of Minus crude oil (100 wt% of the fraction has a boiling point higher than 520 ° C) to 2 wt%, after which the feed oil was thoroughly stirred and fed to the reactor The reactor and reaction conditions were the same as in Example 1, while the stationary operating state was maintained for 20 hours andhad.

The test could be run stably without clogging the reactor, the conversion being 80.9 wt% and the yield of the liquid fraction having a boiling point below 520 ° C over 74.9 wt%. The amount of coke formed was 1.2 wt%, while the amount of coking on the surface of the inner wall of the reactor was 95 ppm based on the total weight of the feed fed. Example XIII

The product oil obtained in Example 1 was subjected to atmospheric distillation and vacuum distillation to remove the fraction having a boiling point below 520 ° C. The resulting residue * was filtered under heating. The solid residue was after extraction of the filtered product with tetrahydrofuran. dried and added to a vacuum residue of Minus crude oil (100 wt% of the fraction has a boiling point higher than 520 ° C) to 4 wt%, followed by addition of 0.5 wt% of a dispersant, consisting essentially of calcium petroleum sulfonate. The mixture was stirred vigorously and fed into the reactor. The reactor and reaction conditions were the same as in Example 1, the run being run at idle for 30 hours.

It was found that the test could be run stably without clogging the reactor, the conversion being 81.8 wt% at a yield of liquid fraction having a boiling point below 520 ° C of 75.4 wt%. The amount of coke formed was 1.6% by weight and the amount of coke on the surface of the inner wall of the reactor was 140 ppm, based on the total weight of the feed oil supplied.

Example XIV

The product oil obtained in Example 1 was subjected to atmospheric distillation and vacuum distillation to remove the fraction having a boiling point below 520 ° C. The resulting residue was added to a vacuum residue of Minus crude oil (100 wt% of the fraction has a boiling point higher than 520 ° C) to 4 wt%, after which molybdenum naphthenate in an amount of 500 ppm, calculated as molybdenum, based to the feed oil was added, as well as further 0.5 wt.% silica, obtained by a vapor phase process (average particle size 8 µm (EM method), specific surface area: 350 m / g (BET method)). The mixture was stirred vigorously and fed into the reactor. The reactor and the reaction conditions were the same as in Example 1, the test being run stationary for 30 hours. It was found that the test could be run stably without the reactor clogging at 74.8 wt% conversion, and a yield of liquid fraction with a boiling point below 520 ° C of 69.7% by weight. The amount of coke formed was 2.0 wt% and the amount of coking on the surface of the inner wall of the reactor 35 was 180 ppm based on the total weight of the oil fed.

«8402008 -29-

Example XV

With a vacuum residue of Taching crude oil (100 wt% of the fraction has a boiling point higher than 520 ° C) as the feed oil, a thermal cracking process was carried out using the same continuous type 5 apparatus, which was used at Example 1 as in Example I. .

The components fed to the feed oil were copper naphthenate in an amount of 500 ppm, calculated as copper and silica formed by a liquid phase process (average particle size: 2 15 wy .. (EM method), specific surface area: 210 m / g (BET method)) jq up to an amount of 2% by weight. The feed oil was thoroughly stirred before being fed into the reactor.

Reaction conditions used for the thermal cracking were o 2 a temperature of 490 ° C, a pressure of 150 kg / cm, a residence time (based on cold liquid) of 20 minutes and a hydrogen / feed 2 oil ratio of 2000 Nl / 1, whereby the number of revolutions of the stirrer was 1000 revolutions per minute. The stationary state was maintained for 50 hours.

It was found that the test could be run stably without clogging the reactor, the conversion being 81.4 wt% and the yield of the liquid fraction boiling below 520 ° C

76.0 wt%. The amount of coke formed was 1.4% by weight and the amount of coking on the surface of the inner wall of the reactor was 20 ppm based on the total weight of the feed oil. The amount of hydrogen used was found to be 100 Nl / kg feed.

Example XVI

Using a vacuum residue of Arabian light crude oil (100% by weight of the fraction has a boiling point higher than 520 ° C) as the feed oil, thermal cracking was performed with the same continuous type installation operating at high pressure as used in Example I.

2Q Components supplied to the feed oil were vanadium acetylacetonate in an amount of 500 ppm as vanadium and further silica produced by evaporation phase process (average particle size: 12 mtji (EM method), specific surface area: 230 m / g (BET method)) up to an amount of 3% by weight. The feed was stirred vigorously before being fed to the reactor.

The reaction conditions o 2 used for the thermal cracking were a temperature of 480 ° C, a pressure of 200 kg / cm, a residence time (based on cold liquid) of 25 minutes and a hydrogen / 8402008

* · „V

Feed oil ratio of 2000 Nl / l, the stirrer speed being 1000 rpm. The stationary state was maintained for 100 hours.

It was found that the test could be run stably without clogging the reactor, the conversion being 74.7% by weight and the yield of the liquid fraction having a boiling point below 520 ° C.

68.9 wt%. The amount of coke formed was 1.0 wt% and the amount of coking on the surface of the inner wall of the reactor was 200 ppm based on the total weight of the feed oil. The amount of hydrogen used was found to be 170 Nl / kg feed. Example XVII

Using a vacuum residue of Venezuelan crude oil (100 wt% of the fraction has a boiling point higher than 520 ° C) as the feed oil, thermal cracking was performed by the same continuous type device operating at high pressures as used in example I.

The following components were fed to the feed oil, nickel naphthenate in an amount of 500 ppm as nickel and further silica produced by a liquid phase process (average particle size: 15 (EM method), specific surface area: 210 m / g (BET- method)} to a content of 2% by weight The feed was stirred vigorously before being fed into the reactor.

Reaction conditions used for the thermal cracking were a temperature of 485 ° C, a pressure of 200 kg / cm 2, a residence time (based on cold liquid) of 25 minutes and a hydrogen / feed oil ratio of 2000 Nl / l, where the number of revolutions of the stirrer was 1000 revolutions per minute. The stationary state was maintained for 20 hours.

It was found that the test could be run stably without reactor clogging occurring, the conversion being 78.2 wt% and the yield of the liquid fraction having a boiling point below 520 ° C 71.9 wt% amount. The amount of coke formed was 2.8 wt% and the amount of coking on the surface of the inner wall of the reactor was 240 ppm based on the total weight of the feed. The amount of hydrogen used was found to be 190 Nl / kg feed.

8402008 -31-

Example XVIII

Using a vacuum residue from Maya crude oil (100 wt% of the fraction has a boiling point higher than 520 ° C) as feed oil, thermal cracking was performed by the same continuous type device operating at high pressures as used in example I.

The following components were added to the feed oil: nickel naphthenate in an amount of 500 ppm as nickel, and further silica produced by liquid phase process (average particle size: 15 my (EM method), specific surface area: 210 m / g (BET method)) to a content of 2% by weight. The feed was thoroughly stirred before being added to the reactor.

Reaction conditions used for the thermal cracking were a temperature of 485 ° C, a pressure of 200 kg / cm, a residence time (based on cold liquid) of 25 minutes and a hydrogen / feed oil ratio of 2000 Nl / l, whereby the number of revolutions of the stirrer was 1000 revolutions per minute. The stationary state was continued for 20 hours.

The test was found to be able to run stably without clogging the reactor, the conversion being 75.4 wt% and the yield of the liquid fraction having a boiling point below 520 ° C.

68.1 wt%. The amount of coke formed was 2.7% by weight and the amount of coking on the surface of the inner wall of the reactor was 280 ppm, based on the total weight of the tour oil. The amount of hydrogen consumed was found to be 220 Nl / kg feed.

♦

Example XIX

A mixture of all product oils of Examples I-V and X-XIV

were used as the feed oil. By means of a continuous type hydrotreater reactor with an internal diameter of 30 18 mm, where the fixed bed reactor was packed with Ni-Mo / Al catalyst 2 with a specific surface area of 270 m / g and a porosity of 0.75 ml / g containing 5 wt.% nickel oxide and 20 wt.% molybdenum oxide, after pre-sulfidation of the catalyst, the hydrogenation was carried out under the reaction conditions: hydrogen / feed oil ratio of 1000 Nl / l, temperature of 400 ° C , a pressure of 180 kg / cm and LHSV of Q, 8 hours.

The properties of the feed oil and the recovered hydrotreated oil 8402008 are shown in Table A.

Example XX

Using a fraction obtained by high boiling. components with a boiling point higher than 520 ° C from the production oil of Example 1 by atmospheric distillation and. vacuum distillation, which served as the feed oil, and Co-Mo / Al 2 catalyst with a specific surface area of 240 m / g and a porosity of. 0.53 ml / g, containing 4 wt% cobalt oxide and 14 wt% molybdenum oxide, after pre-sulfidation, hydrotreating was performed by the same continuous type hydrotreating reaction plant used in Example XIX, under the following reaction conditions: hydrogen / feed oil ratio 1000 Nl / 1, temperature 390 ° C, a pressure 2-1 of 150 kg / cm and LHSV 1.0 hour. The properties of the feed oil and the recovered hydrotreated oil are shown in table. A indicated.

Example XXI

Using a fraction obtained by removing high-boiling components having a boiling point higher than 520 ° C from the product of Example XVI by atmospheric distillation and vacuum distillation, which fraction is used as the feed oil, and Ni-Mo / 20 Al catalyst with a specific surface area of 230 m / g and a porosity of 0.60 m / g containing 4 wt% nickel oxide and 14 wt% molybdenum oxide, after pre-sulfidation, hydrotreating was carried out using the same continuous type hydrotreater as used in Example XIX under the following reaction conditions: hydrogen / feed oil ratio 1000 Nl / l, temperature 400 ° C, 2 -1 pressure 200 kg / cm and LHSV 0.8 hours. The properties of the feed oil and the recovered hydrotreated oil are shown in Table A. 30 8402008 · »

-33-TABLE A

Changes in oil properties due to hydrotreating

Example XIX__Example_XX Example XXI

supply * hydrobe supply hydrobe supply hydrobe-treated trade-traded oil oil oil specific gravity 0.8490 0.8100 0.8327 0.8048 0.8703 0.8358 (15 / 40C) H / C (atomic ratio) 1, 79 1.95 1.88 1.99 1.69 1.92 sulfur content (wt%) 0.05 trace 0.02 trace 2.31 0.01 nitrogen content 0.12 0.05 0.05 0. 02 0.06, 0.01 (wt%) |

Conradson carbon 6.40 0.02 0.07 trace 0.15 trace residue (wt%)

Type of analysis (column-15 chromatography) saturated compo 75.0 91.5 79.3 93.0 55.2 91.1 n (wt%) aromatic compo 18.9 8.3 15.7 6.9 39.4 8.4 nent (wt%) polar components 6.1 0.2 5.0 0.1 5.4 0.5 20 (wt%)

Hydrogen distribution (H-NMR) aromatic water 3.9 1.1 3.2 1.0 6.1 1.3 dust (%) _ olefinic water 1.1 trace 1.0 trace 1.4 trace "dust (%) aromatic α position 6.0 4.8 5.8 4.8 12.8 7.2 hydrogen (%) methylene water 66.4 69.3 65.8 69.5 55.5 66.4 substance (%) ^ methyl water- 22.6 25.0 24.2 24.7 24.2 ~ 25.1 ^ dust (%) ~ ^ -----— i σ

Example XXII

From the thermally cracked product of Example 1, from which the gaseous components had been removed, the high-boiling components having a boiling point above 520 ° C were removed by atmospheric and vacuum distillation. The fraction having a boiling point lower than 52 ° C was steam pyrolysed by means of a tubular heater «__ __ 8402008 r« -34- type pyrolysis inridating under the following conditions: inlet temperature 550 ° C, outlet temperature 830 ° C, an outlet pressure of 0.8 kg / cnn (gauge pressure), steam oil weight ratio of 1.0 and a residence time of 0.2 seconds, whereby olefins and monocyclic aromatics were obtained.

The results of the steam pyrolysis along with the yields of the major chemical starting materials (major gaseous olefins and monocyclic aromatics) per feed of the vacuum residue of Minus crudes are shown in Table B.

Example XXIII

The hydrotreated oil from which the gaseous components had been removed, obtained according to Example XX using the Minus vacuum residue as the starting material, was subjected to steam pyrolysis in the manner of Example XXII at the following conditions inlet temperature 550 ° C, outlet temperature 830 ° C C, 2 outlet pressure 0.8 kg / cm (gauge pressure), steam / hydrotreated oil weight ratio 1.0 and residence time 0.2 seconds to yield olefins and monocyclic aromatics.

The results of the steam pyrolysis along with the yields of the major chemical starting materials (major gaseous olefins and monocyclic aromatics) per feedstock are shown in Table B.

Comparative example 7

The thermally cracked product obtained in the stable test of Comparative Example 1, from which the gaseous components had been removed, was subjected to atmospheric and vacuum distillation in the separation step, after which the fraction boiling point below 520 ° C was subjected to the hydrotreating step and the steam pyrolysis step as in Examples XX and XXIII.

The results of the steam pyrolysis, together with the yields of the main chemical starting materials (main gaseous olefins and monocyclic aromatics) are shown in Table B.

Comparative Example 8 The thermal cracking step was performed using the vacuum of Minus crude oil as the feedstock, using the same hydrotreating equipment as in Example XIX at the following conditions: Ni-W catalyst at 70 Silica wt / 30 wt% alumina 2 with a specific surface area of 230 m / g and a porosity of 0.37 ml / g containing 6 wt% nickel oxide and 19 wt% tungsten oxide, a temperature of 380 ° C, a reaction pressure of 200 kg / cm 2 (gauge pressure), LHSV 0.5 h 1 and a hydrogen / feed oil ratio of 2000 Nl / 1, which represents conditions in which the catalyst activity does not deteriorate significantly at the beginning of the test. The yield of the liquid fraction with a boiling point below 520 ° C, 10 was only 16.5% by weight. The resulting liquid fraction was subjected to the same steam pyrolysis step as in Example XXII.

The results of the steam pyrolysis, together with the yields of the major chemical starting materials (major gaseous olefins and monocyclic aromatics) per feedstock are reported in Table II.

As can be seen from the results of Examples XXII and XXIII and Comparative Examples 7 and 8, the process of the invention is an excellent process for decomposing heavy hydrocarbons to feedstock which can be used for steam pyrolysis and give high yields of petrochemical feedstock. Example XXIV

From the thermally cracked product obtained in Example XV, from which the gaseous components had been removed, using the vacuum residue of Taching crude as feed material, the high boiling components having a boiling point higher than 520 ° C were removed by atmospheric and vacuum distillation .

The fraction having a boiling point below 520 ° C was pyrolysed by steam using a tubular heat-type pyrolizer under the following conditions: inlet temperature 550 ° C, outlet temperature 830 ° C, outlet pressure 0.8 kg / cm ^ ( overpressure), steam oil weight ratio 1.0 and residence time 0.2 seconds, whereby olefins and monocyclic aromatics are obtained.

The results of the steam pyrolysis along with the yield of the major chemical starting materials (major gaseous olefins and monocyclic aromatics) per feedstock are reported in Table B.

8402008 * r »-36-

Example XXV

From the thermally cracked product, from which the gaseous components had been removed, obtained in Example XVI using the vacuum residue of Arabian light crude oil as feed material, the high boiling components having a boiling point higher than 520 ° C were removed by atmospheric and vacuum distillation removed.

The fraction having a boiling point below 520 ° C was pyrolysed with steam in a tubular heater-type pyrolizer under the following conditions: inlet temperature 550 ° C, outlet temperature o 2 10 830 C, outlet pressure 0.8 kg / cm (gauge pressure), steam oil weight ratio 1.0 and residence time of 0.2 seconds to obtain olefins and monocyclic aromatics.

The results of the steam pyrolysis together with the yields of. the main chemical starting materials (gaseous olefins and monocyclic aromatics) per feedstock are listed in Table B.

Example XXVI

The hydrotreated oil, from which the gaseous components had been removed, obtained in Example XXI using the vacuum residue of Arabian light crude as feed material, was pyrolysed by steam in a tubular heater-type pyrolizer under the following conditions: inlet temperature 550 ° C, outlet temperature 830 ° C, outlet pressure 0.8 kg / cm 2 (gauge pressure), steam / hydrogenated oil weight ratio 1.0 and residence time 0.2 seconds to obtain olefins and monocyclic aromatics.

The results of the final stage, in which the hydrogenated oil was subjected to steam pyrolysis, are reported in Table B together with the yields of the main chemical starting materials (gaseous olefins and monocyclic aromatics) per feedstock.

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Examples XXVII-XXX

The thermally cracked products obtained in resp. examples XI / XII, XIII and XIV, from which the gaseous components had been removed, were each in resp. Examples XXVII, XXVIII, XXIX and 5XXX were used as the hydrocarbon oil, which was thermally cracked into lighter products, each oil being subjected to atmospheric and vacuum distillations in the respective separation steps to remove components boiling above 520 ° C.

Each of the hydrocarbon oils / whose high boiling components having a boiling point above 520 ° C had been removed was hydrotreated similar to Example XX.

Any hydrotreated oil from which the gaseous components had been removed were subjected to steam pyrolysis similar to Example XXII.

The results of the steam pyrolysis, together with the yields of the major chemical starting materials (gaseous olefins and mono-cyclic aromatics) per vacuum residue of Minus crude, which is the starting material, are reported in Table C.

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Examples XXXI and XXXII

Using an atmospheric residue of Minus crude oil (100 wt% of the fraction has a boiling point higher than 343 ° C, 45 wt% a boiling point higher than 520 ° C) as feedstock, the same continuous type of installation operating at high pressures as in thermal cracking as in Example I.

The two types of components to be added thereto the thermal cracking of the feedstock were the following: molybdenum naphthenate in an amount of 100 ppm calculated as molybdenum and 10. furnace soot (average particle size: 15 my (EM method), specific surface area: 200 m ^ / g (BET method)) in an amount of 2 wt%, for example XXXI, an aqueous solution of ammonium molybdate dissolved in water in an amount of 500 ppm, calculated as molybdenum to form an emulsion, further alumina, produced by a vapor phase process, was added (average particle size 2: 20 my (EM method), specific surface area: 100 m / g (BET method)) in an amount of 3 wt% for example XXXII.

The thermal cracking conditions were in both cases: temperature 490 ° C, pressure of 150 kg / cm, residence time (based on 20 cold liquid) 18 minutes and hydrogen / feed ratio 1500 Nl / 1, whereby the number of stirrer revolutions was 1000 revolutions per minute. used to be.

The thermally cracked products freed from gaseous components were each subjected to atmospheric and vacuum distillations in the separation step similar to Example XX to remove high boiling components having a boiling point higher than 520 ° C, the fraction having a boiling point lower then 520 ° C with steam was pyrolyzed to olefins and monocyclic aromatics.

The steam pyrolysis results of Examples XXXI and XXXII are set forth in Table D, together with the yields of the major chemical starting materials (gaseous olefins and monocyclic aromatics).

Examples XXXIII and XXXIV

Using an atmospheric residue of Arabian light crude oil (100 wt% of the fraction has a boiling point higher than 343 ° C, 46 wt% boiling point higher than 52 ° C) as feed material, thermal cracking was performed by of the same continuous-type installation 8402008 /? * * -41- operating at high pressures, as in example I.

In the thermal cracking, the following two types of compounds were added to the feed oil: iron pentacarbonyl in an amount of 800 ppm, calculated as iron and channel carbon black (average 5 part size: 14 ny (EM method), specific surface area: 300 m / g ( BET method)), in an amount of 2 wt. % in the case of Example XXXIII, cobalt resin in an amount of 300 ppm calculated as cobalt and thermal carbon black (average particle size: 80 m ^ i (EM method), specific surface area: 15 m2 / g (BET method)) in an amount 10 wt% in the case of Example XXXIV.

The thermal cracking conditions in both cases were: temperature 470 ° C, pressure 200 kg / cm 2, residence time (based on cold liquid) 30 minutes and hydrogen / feed oil ratio 2000 Nl / 1, the number of stirrer revolutions being 1000 revolutions per minute.

The thermally cracked products freed from gaseous components were each subjected to atmospheric and vacuum distillations in the resp. separating step to remove high-boiling components with a boiling point higher than 520 ° C.

Using the fraction having a boiling point of less than 20 520 ° C, obtained as the feed oil, hydrotreating was carried out using the same continuous type hydrotreating reaction plant and fixed bed catalyst as in Example XIX under the following conditions: hydrogen / feed oil ratio 1000 Nl / 1, 0 -1 temperature 395 C, pressure 180 kg / cm and LHSV 0.8 hours.

The recovered hydrotreated oil was steam pyrolyzed by means of a tubular heater type pyrolizer at an inlet temperature of 550 ° C, an outlet temperature of 830 ° C, an outlet 2 pressure of 0.8 kg / cm (gauge pressure) , a steam / hydrogenated oil weight ratio of 1.0 and a residence time of 0.2 seconds to prepare olefins and monocyclic aromatics.

The steam pyrolysis results of Examples XXXIII and XXXIV are reported in Table D, together with the yields of the major chemical materials (gaseous olefins and monocyclic aromatics).

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Claims (11)

Method for converting a heavy hydrocarbon into a more valuable product, characterized in that at least two types of materials are added to the heavy hydrocarbon, consisting of an oil-soluble or water-soluble transition metal compound and an ultra-fine powder, which can be suspended in a hydrocarbon, with an average particle size in the range of 5-1000 myr, after which the heavy hydrocarbon is thermally cracked in the presence of hydrogen gas or a hydrogen sulfide-containing hydrogen gas and the resulting lighter hydrocarbon oil is recovered. A method for converting the heavy hydrocarbon into a more valuable product, characterized in that: an oil-soluble transition metal compound is dissolved in an oil or an aqueous solution of a water-soluble transition metal compound in an oil is emulsified; an ultra-fine powder with an average particle size in the range of 5-1000 µm is dispersed in the oil solution or in the oil / aqueous solution; the dispersion is heated at the decomposition temperature of the transition metal compound in the presence of hydrogen or a hydrogen sulfide-containing hydrogen gas; a solid is separated from the dispersion; the solid is added to a heavy hydrocarbon oil; the heavy hydrocarbon is thermally cracked in the presence of hydrogen gas or a hydrogen sulfide-containing hydrogen gas and the resulting lighter hydrocarbon oil is recovered. 3. A method of converting a heavy hydrocarbon into a more valuable product, characterized in that an oil-soluble transition metal compound is dissolved in an oil or a water-soluble transition metal compound is dissolved in water; the solution is converted into a solid by spraying the solution into hydrogen gas or a hydrogen sulfide-containing hydrogen gas in which an ultra-fine powder having an average particle size in the range of 5-1000 µm is dispersed and simultaneously heating the gas to to decompose the transition metal compound and dry the solid; the solid obtained is added to a heavy hydrocarbon; the heavy hydrocarbon is in. the presence of hydrogen gas or a hydrogen sulfide-containing hydrogen gas is thermally cracked and the resulting lighter hydrocarbon oil is recovered. 8402008 1 & * -44- Process according to claims 1 to 3, characterized in that the solid separated from the lighter hydrocarbon oil and recovered in whole or in part or a residue obtained by distilling the lighter hydrocarbon is recycled. Process according to claims 1-3, characterized in that the residue obtained by distilling the lighter hydrocarbon is wholly or entirely. part is recycled. 6. Process for converting a heavy hydrocarbon into a lighter and more valuable product, characterized in that the lighter hydrocarbon oil obtained according to claims 1,2, 3, 4 or 5 is hydrotreated (hydrotreated) ) and the obtained hydrotreated oil is recovered. 7. A process for converting a heavy hydrocarbon into a lighter and more valuable product, characterized in that a high boiling fraction is removed from the lighter hydrocarbon oil obtained according to claim 1, 2, 3, 4 or 5, a low boiling fraction under hydrotreating conditions is hydrotreated (hydroprocessed) and the resulting hydrotreated oil is recovered. Method for converting a heavy hydrocarbon into a more valuable product, characterized in that: (A) adding to a heavy hydrocarbon (i). at least two kinds of materials comprising an oil-soluble or water-soluble transition metal compound and an ultra-fine powder which can be suspended in a hydrocarbon and has an average particle size in the range of 5-1000 µm; or (ii) a solid resin prepared by dissolving an oil-soluble transition metal compound in an oil or emulsifying a water solution of a water-soluble transition metal compound in an oil; Dispersing an ultra-fine powder of average particle size in the range of 5-1000 µm in the oil solution or in the oil / aqueous emulsion; and heating the dispersion to the decomposition temperature of the transition metal compound in the presence of a hydrogen gas or a hydrogen sulfide-containing hydrogen gas; or 35 (iii) a solid prepared by dissolving an oil-soluble transition metal compound in an oil or dissolving a water-soluble transition metal compound in water; and converting the solution into a dry solid by spraying the solution into a hydrogen gas or a hydrogen sulfide-containing hydrogen gas in which an ultrafine powder having an average particle size in the range of 5-1000 µm is dispersed and by simultaneously heating the gas to decompose the transition metal compound and to dry the solid; (B) thermally cracking the heavy hydrocarbon in the presence of a hydrogen gas or a hydrogen sulfide-containing hydrogen gas and recovering the resulting lighter hydrocarbon oil; (C) removing a high boiling point fraction from the lighter hydrocarbon oil and (D) pyrolysing a low boiling point fraction or a mixture of the fraction and a petroleum fraction with steam, and recovering a gaseous olefin product and a monocyclic aromatic product. A method for converting a heavy hydrocarbon into a lake where the solid product, characterized in that it comprises: (Ά) adding to a heavy hydrocarbon (i) at least two kinds of materials, comprising an oil-soluble or water-soluble transition metal compound and an ultrafine powder, which can be suspended in a hydrocarbon with an average particle size in the range of 5-1000 µm; or (ii) a solid prepared by dissolving an oil-soluble transition metal compound in an oil or emulsifying an aqueous solution of a water-soluble transition metal compound in an oil; dispersing an ultra-fine powder having an average particle size in the range of 5-1000 µm in the oil solution or in the oil / aqueous emulsion; and converting the dispersion to a solid by heating the dispersion to the decomposition temperature of the transition metal compound in the presence of a hydrogen gas or a hydrogen sulfide-containing hydrogen gas; or (iii) of a solid prepared by dissolving an oil-soluble transition metal compound in an oil or dissolving a water-soluble transition metal compound in water; and converting the solution to a dry substance by dissolving the solution in hydrogen gas or hydrogen 8402008 -¾ β. Spray 5 * -46- sulfide-containing hydrogen gas in which an ultrafine powder having an average particle size in the range of 5-1000 µm is dispersed and by simultaneously heating gas to decompose the transition metal compound and to dry the solid-5; (B) thermally cracking the heavy hydrocarbon in the presence of hydrogen gas or a hydrogen sulfide-containing hydrogen gas and recovering the resulting lighter hydrocarbon oil; (C) removing a high boiling fraction from the lighter hydrocarbon oil; (D) hydrotreating a low boiling fraction under hydrotreating conditions and recovering the resulting hydrotreated oil; and (pyrolysing the hydrotreated oil or a mixture of the hydrotreated oil and a petroleum fraction with steam, and recovering a gaseous olefin product and a monocyclic aromatic product. 10. Process according to claim 8 or 9, characterized in that a solid separated and recovered from the lighter hydrocarbon oil obtained in step (B) or the high boiling fraction is removed in step (C) completely or part of it is recycled to stage (B). Process according to claim 8 or 9, characterized in that the high boiling fraction removed in stage (C) is recycled in whole or in part to stage (B). 25 8402008