FR2556000A1 - Process for converting a heavy hydrocarbon into a product of higher value or a lighter one - Google Patents

Abstract

Process for converting a heavy hydrocarbon into a product of higher value. According to the invention at least two kinds of substances are added to a heavy hydrocarbon, comprising a transition metal compound which is soluble in oil or in water and an ultrafine powder which can be suspended in a hydrocarbon and whose mean particle size is between 5 and 1000 <0>m; the heavy hydrocarbon is cracked thermally in the presence of gaseous hydrogen or of gaseous hydrogen containing hydrogen sulphide; and the resulting light hydrocarbon oil is recovered; use is made of thermal cracking equipment 3, a gas-liquid separator 5, an atmospheric washer 8, a vacuum washer 10, hydrotreatment equipment 20, a high-pressure gas-liquid separator 23, a gas-liquid separator 26 and steam-pyrolysis equipment 29. The invention applies especially to the production of gaseous olefins and of monocyclic aromatic products.

Description

The present invention relates to a process for converting a heavy hydrocarbon, in particular a heavy oil such as an atmospheric residue or a vacuum residue of crude oils, into a lighter and mainly more valuable product, as well as a process for the further hydrotreatment in hy oil
lighter fuel and also to a process for the production of gaseous olefins and products. monocyclic aromatics from a heavy hydrocarbon as a feedstock, using these methods.

In recent years, in addition to the trend to convert crude oils into oils or heavy oils, the imbalance between demand and supply of petroleum products accompanied by the increase in demand for lighter oils poses social problems, and the efficient use of excess heavy oils is nowadays evidence of critical importance in the petroleum industry.

On the other hand, in the production of gaseous olefins such as ethylene, propylene, butadiene, etc., and monocyclic aromatics such as benzene, toluene, xylene etc., mainly light hydrocarbons have been used. such as oil field gases or petroleum refinery by-products like naphtha. These are presently lacking, their price is increasing, and the economic benefits of obtaining gaseous diolefins or monocyclic aromatics are dropping remarkably. To solve such a problem relating to the structure of industries, various attempts have recently been made to produce petrochemical raw materials by hydrotreating lighter oils such as kerosene, gasoline, vacuum gas oils, etc. , followed by steam pyrolysis. However, in these methods, various kinds of oils employed for the feedstock are available as petroleum products, and the situation of supplying raw materials is the same as in the case of
a light hydrocarbon such as naphtha.

Thus, in both petroleum and petrochemical industries, it is now important to convert a heavy oil into a lighter and more valuable product for efficient use as light petroleum products or as raw materials. for petroleum chemistry. Accordingly, a number of processes have been proposed for the hydrocracking or thermal cracking of heavy oils, but none of these processes is satisfactory for the conversion of a heavy oil as a residue under vacuum into a more product. lightweight, as there are certain 'drawbacks.

For example, in a fixed bed or fluidized bed hydrocracking process where the reaction is carried out in a reactor packed with a granulated or powdered catalyst, when a high conversion to a lighter product is effected, the carbon and components of Metals byproducts contained in the feed oil gradually settle on the catalyst layer, which can cause depletion of catalyst activity or clogging of the catalyst layer.

Furthermore, if it is desired to achieve a high conversion of a heavy hydrocarbon into a lighter product according to thermal cracking, a phenomenon of coking occurs, which may lead to the operation being stopped. Therefore, this process is generally only applicable for conversion to a lighter product if such coking is not a problem.

For the improvement of this point, the hydrobiscacking process has been proposed. However, this process cannot give a sufficient coking inhibiting effect even if the hydrogen pressure is increased to a high pressure of 300 bar. The one-unit coking process is also provided, where conversion to a lighter product is undertaken while positively forming coke. This process, in addition to removing the coke by-product in a large quantity, cannot be exempt from the problem of the reduced yield of light oil.
In addition, the light oil obtained is enriched in aromatic components and olefinic components, and therefore has the disadvantage of being of poor quality.

Thus, in the prior art, even when an attempt has been made to convert a material with a high boiling point into a lighter product by catalytic treatment of a heavy oil, the impurities contained in the oil such as sulfur or metals heavy and in particular the presence of basic polymeric compounds markedly lowered the acidic capacity of the catalyst. This therefore poses a problem because the cracking activity due to the acidity of the catalyst cannot persist.

Likewise, in the thermal cracking of a hydrocarbon in the absence of a catalyst, it is known that the rate of the reaction is greater with the increase in molecular weight. However, since the rates of side reactions such as coke formation and polycondensation are also important, it is very difficult in reaction operations to increase the degree of cracking.

On the other hand, various techniques have been reported for the hydrotreatment of louro hydrocarbons by the reaction in a dispersed state with the addition of solids. US Patent No. 3,131,142, US Patent No. 4,134,825, US Patent No. 4,172,814 and US Pat. No. 4,285,804 discloses hydrotreatments by adding an oil soluble metal compound or an emulsion of an aqueous solution of a water soluble metal compound.

US Patent No. 3,161,585 and US Patent No. 3,657,111 disclose hydrotreatments using thermally cracked colloidal material of an oil-soluble metal compound or colloidal particles of vanadium sulfides. Canadian Patent No. 1,073,389, Canadian Patent No. 1,076,983, US Patent No. 4,176,051, US Patent No. 4,214,977 and US Patent No. 4,376,695 disclose hydrocracking using pulverized or carbonated coal. Pulverized coal coated with a metallic salt. US Patent No. 3,707,461 and US Patent No. 4,299,685 disclose hydrotreatments using pulverized coal ash. US Patent No. 4,169,038, US Pat.
US Patent No. 4,178,227, US Patent No. 4,204,943, Japanese Patent Publication No. 207688/1982 and Japanese Patent Publication No. 69289/1983 disclose hydrotreatments using byproduct coke or petroleum ash under produced. Japanese Patent Publication No. 40806/1979 and Japanese Patent Publication No. 141388/1981 disclose hydrocracking using a desulfurized catalyst or its pulverized spent catalyst. US Patent No. 4Q66,530 and US Patent No. 4,067 799 discloses a hydrotreatment using a combination of an oil soluble metal compound and a particle of an iron component, Japanese Patent Publication No. 108294/1983 using a combination of a metal compound and a metal-containing by-produced dust, and US Patent No. 3,331,769 and US Patent No. 4,376,037 using a combination of a metal compound and a porous solid catalyst or porous support, respectively. However, in most of these techniques, reactions close to the conditions of desulfurization are employed, and they are proposals mainly aimed at the removal of metals, the removal of heteroatoms such as the removal of sulfur or nitrogen. e or the removal of residual carbon from heavy hydrocarbons.

In one part of these techniques, a heavy hydrocarbon which can be relatively easily cracked as a feedstock is employed and is used.
attempt to apply an appropriate degree of hydrocracking using residual catalyst, coke byproducts or a natural product. Thus, according to these techniques, during an application to the high conversion of heavy hydrocarbon5 such as the atmospheric residue or the vacuum residue in lighter products, the technical problems concerning practical aspects such as the plugging of the equipment and the economic problems remain. to solve.

The present inventors have made intensive studies to overcome the drawbacks of the prior art processes and to develop a process for converting a heavy hydrocarbon as a feedstock into a lighter and higher value product. economically and in high efficiency. Accordingly, it has now been found that by adding at least two kinds of components of an oil-soluble or water-soluble transition metal compound and d '' an ultra-fine powder having an average particle size between 5 and 1000 mp, which can be suspended in a hydrocarbon, to the feedstock of a heavy hydrocarbon and by carrying out thermal cracking in the presence of hydrogen gaseous or hydrogen gas containing hydrogen sulphide, the side reactions of polycondensation and coke formation could be suppressed and the formation of deposits (coking) in the equipment, in part especially in the reaction zones, could be inhibited, thereby enabling light oils to be obtained economically, stably and in high yield from a heavy hydrocarbon while at the same time suppressing deterioration of the residue to reduce its amount remarkably. The present invention is based on this finding.

More particularly, the present invention relates to a process for converting a heavy hydrocarbon into a higher value product which consists of:
adding to the heavy hydrocarbon at least two kinds of substances comprising an oil-soluble or water-soluble transition metal compound and an ultra-fine powder which can be suspended in a hydrocarbon and with an average particle size of 5-1000
thermally crack heavy hydrocarbon in the presence of hydrogen gas or hydrogen gas containing hydrogen sulfide
recovering the resulting light hydrocarbon oil.

The invention will be better understood, and other objects, characteristics, details and advantages thereof will emerge more clearly during the explanatory description which follows given with reference to the appended schematic drawings given solely by way of example illustrating several embodiments of the invention, and in which
Figures 1 and 2 show functional diagrams of the various embodiments of the process for producing gaseous olefins and monocyclic aromatics, respectively, according to the invention.

In Figures 1 and 2, 3 is a cracking heater, 5 is a high pressure gas-liquid separator, 8 is an atmospheric rinser, 10 is a vacuum rinser, 17 is a liquid-solid separator, 20 shows hydrotreating units, 23 is a high pressure gas-liquid separator, 26 is a gas-liquid separator and 29 is a steam pyrolysis unit.

The heavy hydrocarbon to be used in the present invention is a crude oil or an atmospheric residue or a vacuum residue of a crude oil, also comprising shale oil, extract of asphalt sand and oil. heavy liquefied coal oil. A heavy hydrocarbon containing a large amount of a useful fraction resulting in a high conversion of heavy oil to a lighter product of greater value, for example, a fraction having a boiling point of 5200C or more at pressure atmospheric, has great economic effects.

In the process of converting a heavy oil to a lighter and more valuable product according to the present invention, a synergistic effect can be produced by using at least two kinds of substances in combination. It can be considered that it is presented due to the action described below.

An oil soluble or water soluble transition metal compound can be considered to be converted by heat treatment in the presence of hydrogen and / or hydrogen sulfide in the heavy hydrocarbon reaction zone. or at the stage before that, in a substance having hydrotreating catalytic activity into a hydrocarbon to thereby inhibit the polycondensation reaction or the coke or coke precursor formation reaction which are inevitable side reactions in the high conversion of 'a heavy hydrocarbon to a lighter and higher value hydrocarbon. In addition, other advantages are shown such as suppressing the amount of the by-product gases, preventing or deteriorating the properties of the oil produced by thermal cracking, and the like.

On the other hand, an ultra-fine powder having an average particle size of between about 5 and 1000 mr, which can be suspended in a hydrocarbon, can also be considered as preventing the phenomenon of deposit formation.
coking) in the reaction zone, which is also inevitable in the high conversion of a heavy hydrocarbon to lighter and higher value hydrocarbons, ensuring the floating state of the coke precursor, coke or the like or by its capacity to transport and migrate these materials.

Further, when a compound of a transition metal is converted into a substance having catalytic hydrotreating activity, it can be considered to serve to form high dispersibility and high surface area. As a result, there are additional advantages such that the effect can be exhibited with a small amount of the compound of a transition metal and the effect can be exhibited even with a transition metal having a low hydrogenation function. .

In practicing the process for high conversion of a heavy hydrocarbon to lighter and higher value hydrocarbons according to the invention, it is essentially required that at least two kinds of substances of a compound of a metal soluble in oil or soluble in water or a substance having hydrotreating catalytic activity converted from this compound, and an ultrafine powder having an average particle size of between about 5 and 1000 m, are simultaneously present in a heavy hydrocarbon. However, it is not necessary to pre-prepare a specifically mixed mixture, but it is simply sufficient to separately add these substances to a heavy hydrocarbon feedstock. Even when the respective components can be added separately, the compound of a transition metal can be considered to act with the ultra-fine powder for automatic change into a system of substances having a desired function in the reaction zone or at the stage before the reaction. reaction zone. The ultra-fine powder should be suspended in a light hydrocarbon. The "suspension" mentioned herein indicates the state where solid particles exist substantially in a liquid or the state where the solid phases are distributed discontinuously through the liquid phase which is a continuous phase, including what is referred to as colloid, mud or paste.

Of course, it is also possible to prepare, beforehand, a system of substances which can have a desired function with at least two kinds of substances, and to use this system of substances for addition to the feedstock of a. heavy hydrocarbon. For example, 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 gas oil or gas. -oil under vacuum, an ultra-fine powder having an average particle size of between about 5 and 1000 mJu is dispersed in the solution or emulsion. The resulting dispersion is subjected to heat treatment at a temperature at which the compound of a transition metal decomposes in the presence of hydrogen gas or hydrogen gas containing hydrogen sulfide to prepare a solid which is separated or concentrated by a known method of solid-liquid separation and which is added to a heavy hydrocarbon. the heavy hydrocarbon is then used in a process of converting the heavy hydrocarbon into a lighter and higher value product by thermal cracking in the presence of hydrogen gas or hydrogen gas containing hydrogen sulfide. For example, a gaseous phase of hydrogen gas or hydrogen gas containing hydrogen sulfide having an ultra fine powder - with an average particle size of about 5 to 1000 is heated and sprayed into its atmosphere with a an oil solution having an oil soluble transition metal compound dissolved therein or an aqueous solution having a water soluble transition metal compound dissolved therein to decompose the composed of the transition metal, followed by drying. The resulting solid is added to a heavy hydrocarbon which is then subjected to thermal cracking in the presence of either hydrogen gas or hydrogen gas containing hydrogen sulfide to convert the heavy hydrocarbon to lighter and higher value hydrocarbons. However, in the impregnation method or the precipitation method, where the compound of a transition metal is supported on an ultra-fine powder, it is undesirable to use a preparation method where agglomeration or frittaae can occur between mutual compounds of transition metals, between mutual ultra-fine powders, or between the compound of a transition metal and the ultra-fine powder.

As a further system of substances, having a desired function, it is also possible to reuse a thermally cracked product obtained by the present process, to convert a heavy hydrocarbon to a lighter and higher value hydrocarbon or a fractional heavy residue. by distillation of the thermally cracked product as it is or alternatively using a solid separated and recovered from these dispersed oils.

In the compound of an oil-soluble or water-soluble transition metal, the transition metal includes all of the transition elements in Table
Periodic of the Elements and is particularly selected from the group consisting of vanadium, chromium, iron, cobalt, nickel, copper, molybdenum, tungsten, and mixtures thereof.

Examples of the oil-soluble compounds containing desired transition metals are n-complexes containing a cyclopentadienyl group or an allyl group as ligands, organic carboxylic acid compounds, organic alkoxy compounds, diketone compounds such as a diketone complex. acetylacetonate, carbonyl compounds, organic sulfonic acid or organic sulfonic acid compounds xanthinic acid compounds such as dithiocarbamate, amine compounds such as organic diamine complexes, phthalocyanine complexes, compounds nitrile or tisonitrile, phosphine compounds and the like. Particularly preferable oil-soluble compounds are the salts of aliphatic carboxylic acids like stearic acid, octylic acid etc., since they have high solubilities in water. oil, does not contain heteroatom such as nitrogen or sulfur and can be converted relatively easily to an aya substance. has hydrotreating catalytic activity. Compounds of lower molecular weights are preferred, because less can be used for the necessary amounts of the transition metal.

Examples of the water soluble compounds are carbonates, carboxylates, sulfates, nitrates, hydroxides, halides and ammonium or alkali metal salts of transition metal acids such as ammonium theptasolybdenate.

In the case of an oil soluble transition metal compound, it can be used as a solution by adding it directly to the heavy hydrocarbon feedstock. However, in the case of a water soluble transition metal compound, it is necessary to form an emulsion by adding this aqueous solution to the heavy hydrocarbon feedstock. In this case, including the method using an emulsifier, all the known methods of emulsification can be applied.

The ultra-fine powder having an average particle size of between about 5 and 1000 which can be suspended in a hydrocarbon, can exhibit excellent effects as will be described hereinafter in comparison with the solid catalysts, supports used for solid catalysts and simply the ground products thereof, known in the prior art of this field. Indeed, (1) it can guarantee a high dispersibility and a large free movement in the reaction zone and can give a site for a uniform reaction without localization; (2) it will hardly reside in the reaction zone, but will easily discharge the polycondensed products which have adhered or deposited such as asphaltenes, coke precursors, cokes and the like, in a highly dispersed state or floating out of the reaction zone, avoiding thus a plugging in the reaction zone; and (3) it can prevent agglomeration of substances having hydrotreating catalytic activity formed from the compound of a transition metal to effect strong dispersion, thereby improving the activity of the substance having hydrotreating catalytic activity. .

In addition, the greatest characteristic of the ultrafine powder is an extremely large external surface area compared to substantially porous solid catalysts and supports. The solid catalysts and supports according to the prior art, even when they are ground, are widely distributed generally between several microns and a few tens of microns, having a very small external surface. The expected effect is derived mainly from the internal surfaces in the pores. However, in the case where the reaction takes place in the pores, the diffusion rate of the reactants poses a problem, and a gradient of the concentration of the reactants is created between the central part of the particle and the proximity of its surface, the The reaction site therefore becomes non-uniform. As a result, the coefficient of efficiency is always a problem, and physical structures such as the pore distribution or the size distribution of the crushed particles can have important effects on the resulting performance. . In addition, when using a heavy hydrocarbon as a feedstock, substances with large molecular weights which are contained such as asphaltenes, porphyrin-like substances containing heavy metals and coke precursors or cokes formed cannot enter the internal parts of the pores but will easily clog these close to the surface, and the internal surfaces which are substantially dependent on the pores will therefore not be able to function very much, without giving the expected effect. On the contrary, the ultra-fine powder is a system which is not substantially porous or which is not expected to be porous, and it may exhibit a desired effect simply by the effective action of its large outer surface area. will be greatly increased with the decrease in particle size.

For example, in the case of particle sizes of 10 to 50 m t, the surface area can be about 300 to 60 m / g which gives quite an excellent effect.

The ultra-fine powder meeting these properties can be divided into inorganic substances and carbonaceous substances.

Examples of inorganic substances are fine ceramics such as ultra-fine particulate silicic acid, silicates, alumina, titanium oxide and the like, and ultra-fine particles of metals such as those obtained. by the vapor deposition method.

Among these substances, to describe the ultrafine particles of silicic acid and silicates, there is a group of many kinds of substances which are traditionally called white carbon, and they can be synthesized by vapor phase processes such as by Thermal decomposition of silicon halides, thermal decomposition of compounds containing silicic acid, thermal decomposition of organic silicic compounds, etc. ; and according to liquid phase processes such as decomposition of sodium silicate by an acid, decomposition of sodium silicate by an ammonia salt or an alkali salt, formation of a silicate of an alkaline earth metal from sodium silicate followed by decomposition by an acid, ion exchange by treatment of an aqueous solution of sodium silicate with an ion exchange resin, decomposition under pressure of an organogel 1 decomposition of a silicon halide by 'water, decomposition of a solution of sodium silicate by silicofluoric acid byproduct in the step of manufacturing calcium superphosphate, production using natural silicic acid or silicates, reaction of sodium silicate with a hydroxide such as calcium hydroxide or calcium chloride, aluminum chloride or sodium aluminate, processing quartz or silica gel with calcium hydroxide in autoclave, etc. The size of the particles can be measured by an electron microscope and can range from about 5 to 50 mP, although different depending on the kind. With regard to the surface area, the external surface area calculated from the particle size measured by an electron microscope and the specific surface area determined by the gas adsorption method (BET method) substantially coincide, and it is approximately between 50 and 400 m2 / g.

In addition, carbonaceous substances form a group of substances which are obtained by formation of carbon, that is to say carbonization, which can be divided into carbonized substances in the liquid phase or in the solid phase, such as carbonated cokes. petroleum, coal cokes, pitch cokes, activated charcoal, charcoal etc. and substances carbonized in the gas phase such as carbon blacks. Carbonaceous substances, as compared to inorganic substances, are combustible and therefore advantageous when the heavy residue which is a product after the reaction of converting a heavy hydrocarbon to lighter hydrocarbons of greater value is used as fuel for a boiler.

Substances carbonized in phase or liquid
solid phase generally have large formed particle sizes and most of them experience a microspray operation and classification operation in order to have the desired particle sizes. On the other hand, most of the carbonized gas phase substances have particle sizes which are within the particle size range of the present invention, and therefore they are available as is. Among them, the carbon blacks include a large number of particles. variety of kinds formed as carbonized substances in the gas phase, which can be prepared by methods such as the oil-fired method, the gas-fired method, the tunnel method, the thermal method, the oil method. acetylene black, the lamp black method by-product, the lamp black method and others. The particle size can be measured by an electron microscope and is about 9 to 500 mF, although different depending on the kind, about 9 to 100 mi except for the particles produced by the thermal method. With regard to the surface area, the external surface area calculated from the particle size measured by an electron microscope and the specific surface area determined by the gas adsorption method (BET method) coincide substantially, and it is between approximately 5 and 400 m2 / g.

When the ultra-fine powder of the present invention is added to the feedstock of a heavy hydrocarbon, it can be added directly as such or as a concentrated dispersion in a different medium.

The dispersion containing the ultra-fine powder can be subjected to mechanical operation, for example, by a stirrer, an ultra-sonic or a mill, or alternatively or in combination be mixed with dispersing agents such as neutral or basic phosphonate, a salt. metallic such as the salt of calcium or barium sulfonic acid, succinimide and succinate, benzylamine or a polymeric compound of the polypolar type.

In the practice of the process according to the invention for converting a heavy hydrocarbon into a lighter and more valuable product, the amounts of at least two kinds of substances to be added can be between 10 and 1000 ppm, preferably. between 50 and 500 ppm, for the compound of the transition metal calculated as the metal based on the weight of the heavy hydrocarbon feedstock and between about 0.05 and 10% by weight, and better between 0-, 1 and 3% for the ultra-fine powder based on the weight of the heavy hydrocarbon feedstock. In the case of preparing a system of substances which can have the desired function of 'at least two kinds of substances beforehand, it is desirable to prepare a formula having a composition which makes it possible to fall within the ranges specified above. At a threshold of less than 10 ppm of the transition metal in the compound of the transition metal based on the heavy hydrocarbon or at a threshold of less than 0.5% by weight of the ultra-fine powder, one cannot obtain a sufficient effect of inhibiting the side reactions of polycondensation and coke formation, and neither can a sufficient effect of preventing the formation of deposits be obtained
(coking). Moreover, beyond 1000 ppm of the transition metal in the transition compound or beyond 10% by weight of the ultra-fine powder, no further improvement can be recognized corresponding to these amounts, but on the contrary unfavorable side reactions or else solid-liquid separation in the reaction zone and accompanying plugging may occur.

In practicing the process of converting a heavy hydrocarbon into a lighter and higher value product, the thermal cracking conditions depend on the heavy hydrocarbon employed as feedstock and the properties and added amounts of it. 'at least two kinds of substances but in general the reaction temperature employed may be between 400 and 5500C, preferably between 430 and 5200C. In a higher temperature region exceeding this temperature range, thermal cracking will proceed until the formation of cbke and gas production will become considerable until there is noticeably no feedstock left at. convert to lighter oil. On the other hand, in a region of fairly low temperature below this range, the rate of thermal cracking tends to become remarkably slow.

The reaction pressure can be between 30 bars and 300 bars and preferably between 50 bars and 250 bars.

Thermal cracking can be carried out by a batch or continuous system, and the reaction time or the residence time of the heavy hydrocarbon in the reaction can be from 1 minute to 2 hours, preferably from 3 minutes to 1 hour. These processing conditions are not individually optimal values, but they are related to each other and therefore the optimal ranges can be changed depending on the situation. Furthermore, the quantity of hydrogen to be supplied for the practice of thermal cracking can be from 100 to 5000 Nm3 / k1, better still from 500 to 2000 Nm3 / kl, in terms of the volume ratio with respect to the charge d. supply and it is generally desirable to continue to operate with additional hydrogen gas in an amount corresponding to the amount of hydrogen gas consumed. As the hydrogen to be supplied, either high purity hydrogen gas or alternatively high purity hydrogen gas can be employed. a gas mixture containing a large amount of hydrogen gas. Even when employing hydrogen gas containing hydrogen sulfide, the amount to be used may be that corresponding to that above mentioned as the total amount, but the content of hydrogen sulfide may preferably be from i to 10 mole%, approximately.

The type of reaction equipment when carrying out the reaction continuously can be either a tubular reactor, a tower reactor, or a reactor-type reactor, but in each of these reactors it is desirable to perform the reaction. in suspension while maintaining an ultra-fine powder in the suspended state without forming a fixed bed, a fluidized bed or a boiling bed. The structure of the reactor can be simpler for the slurry reaction, and the reaction temperature can be more easily controlled without changing the performance with the passage of time and coking plugging will hardly occur. temperature and a short reaction time can be used relatively easily and therefore a high space velocity can be taken to give a large amount of processing in the unit, with the added advantage of making the chemical consumption amount of hydrogen gas. lower while suppressing hydrogenation activity such as hydrogenation of aromatic rings.

Among the oils produced obtained by the practice of the process of converting a heavy hydrocarbon into a lighter product and of greater value according to the invention, it is possible to have the distillates in their entirety or after fractionation to replace the naphtha in the chemistry of petroleum, or they can be separated into fractions having respective boiling ranges for use as intermediate raw materials
for petroleum products,
like gasoline, jet fuel,
kerosene, diesel fuel, diesel fuel, lubricant and others.

In the process for the further hydrotreatment of the hydrocarbon oil which is obtained as a lighter and more valuable product according to the process of the invention, the resulting hydrocarbon oil can be subjected to a hydrotreatment as it is or after removal by separation of the high boiling point fraction from the obtained hydrocarbon oil. The hydrotreatment can advantageously be carried out after removal of the high-boiling fraction, since substances such as asphaltenes or metals can thus be removed therefrom. In addition, the high boiling fraction removed by separation can be treated substantially in a manner analogous to liquid fuel, which can be used as a fuel source in the process practiced in the present invention or otherwise in the process. boilers in general. As the method of separating the high boiling fraction, conventional high pressure gas separation, atmospheric distillation, vacuum distillation and further solvent deasphalting can be employed.

The catalyst to be used in the practice of the hydrotreatment process can be any catalyst known for the hydrotreatment of petroleum and heavy oil fractions, preferably a catalyst containing at least one kind of metals selected from the metals of the group. VIb and in metals of Group VIII of the Periodic Table such as the kinds of metals nickel-molybdenum, cobalt-molybdenum, nickel-tungsten and the like, supported on a porous inorganic support. These kinds of metals are generally used in the form of oxides or sulfides, and the porous inorganic support may include, for example, alumina, silica, alumincsilicate, zeolite, alumina containing zeolite, alumina-boron oxide, silica-alumina-titanium oxide and the like. Hydrotreatment conditions can be selected as desired depending on the heavy hydrocarbon oil employed as feedstock and the properties of the catalyst, but the reaction temperature may be between 250 to 4800C, preferably between 300 and 4500C. If the reaction temperature exceeds 480 "C, thermal cracking of the side reaction occurs too much, and there is an increase in the carbon deposited on the catalyst, an increase in the hydrogen consumed, which is accompanied by an increase in. production of gas and reduced liquid yield. On the other hand, at a temperature below 250 "C, the rate of the reaction becomes much lower. The pressure of the reaction can be from 3 to 300 bar, preferably from 50 to 250 bars, which is strongly related to the hydrotreating capacity of the catalyst. Furthermore, the liquid hourly space velocity (LHSV) can be from 0.1 to 5.0 h 1, preferably from 0.2 to 3.0 h and the quantity of hydrogen to be introduced is between 200 and 2000 Nm 3. / kl in terms of the volume ratio relative to the feed oil to be hydrotreated. These conditions are not chosen so as to have individually optimum values, but they are related to each other and the optimum ranges should be chosen according to the required conditions, including of course the properties of the feed oil and the feed oil. activity of the catalyst, and also the use for which the hydrotreated oil produced will be intended.

The process for producing gaseous olefins and monocyclic aromatic hydrocarbons using a heavy hydrocarbon as a feedstock comprises, in a first embodiment
(A) addition to a heavy hydrocarbon
(i) at least two kinds of substances comprising an oil-soluble or water-soluble transition metal compound and an ultra-fine powder which can be suspended in a hydrocarbon and which has an average particle size of between 5 and 1000 m; or
(ii) a solid prepared by dissolving an oil-soluble transition metal compound in an oil or by emulsifying an aqueous solution of a water-soluble transition metal in oil by dispersing a powder ultra-fine having an average particle size between 5 and 1000 mp in the solution in oil or in the oil emulsion and heating the dispersion to the decomposition temperature of the compound of the transition metal in the presence of gaseous hydrogen or hydrogen gas containing hydrogen sulphide; or
(iii) a prepared solid dissolving an oil-soluble transition metal compound in an oil or 1dissolving a water-soluble transition metal compound in water and converting the solution into a dry solid by spraying the solution in hydrogen gas or in hydrogen gas containing hydrogen sulphide or an ultra-fine powder having an average particle size between 5 and 1000 mrest dispersed and simultaneously heating the gas to decompose the compound of the transition metal and to dry the solid
(B) thermal cracking of the heavy hydrocarbon in the presence of gaseous hydrogen or aazous hydrogen containing hydrogen sulfide and the recovery of the resulting lighter hydrocarbon oil
(C) removing a fraction having a high boiling point, from the lighter hydrocarbon oil
(D) pyrolysis of a fraction having a low boiling point or of a mixture of the fraction and a petroleum fraction with vapor, and the recovery of a gaseous product of olefins and a monocyclic aromatic product.

Alternatively, according to a second embodiment, the method consists in
(A) add to a heavy hydrocarbon
(i) at least two kinds of substances comprising an oil-soluble or water-soluble transition metal compound and an ultra-fine powder which can be suspended in a hydrocarbon and which has an average size particles between 5 and 1000 my; or
(ii) a solid prepared by dissolving an oil-soluble transition metal compound in an oil or by emulsifying an aqueous solution of a water-soluble transition metal compound in an oil by dispersing a particle. ultra-fine having an average Xe particle size between 5 and 1000 mf in the solution in oil or in the oil / water emulsion and converting the dispersion to a solid by heating the dispersion to the decomposition temperature of the metal of transition in the presence of hydrogen gas or hydrogen gas containing hydrogen sulfide; or
(iii) a solid prepared by dissolving an oil soluble transition metal compound in an oil or by dissolving a water soluble transition metal compound in water; and converting the solution to a dry solid by spraying the solution into hydrogen gas or hydrogen gas containing hydrogen sulfide or an ultra-fine particle having an average particle size between 5 and 1000 m P is dispersed and simultaneously heating the gas to decompose the compound of the transition metal and to dry the solid.

(B) thermally crack the heavy hydrocarbon in the presence of hydrogen gas or hydrogen gas containing hydrogen sulfide and recover the resulting lighter hydrocarbon oil
(C) removing a fraction having a high boiling point, from the lighter hydrocarbon oil
(D) hydrotreating a fraction having a low boiling point under a hydrogenation condition 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 an olefin gas product and a monocyclic aromatic product.

According to a third embodiment of the process, in the process according to the first or second embodiment defined above, all or part of a solid which is separated and recovered from the lighter hydrocarbon oil obtained by step (B) or else the fraction having the high boiling point removed in step (C) is recycled to step (B).

According to a fourth embodiment of the process, in the process according to the first or second embodiment as defined above, all or part of the fraction having a high boiling point, which is removed in step (C), is recycled to step (B).

Thus, the process for producing gaseous olefins and monocyclic aromatics according to the present invention comprises, as basic steps four or five steps. In the case of the four steps, this includes the step of adding to a heavy hydrocarbon, at least two kinds of substances, the thermal cracking step, the step of removing a high boiling fraction and the steam pyrolysis step.

In the case of the five steps, there is the hydrotreatment step between the step of removing a high boiling point fraction and the steam pyrolysis step.

In the thermal cracking step, the process of converting a heavy hydrocarbon to a lighter, higher value product as described above is employed. Accordingly, by the effect of at least two kinds of substances to be added to the feedstock of a heavy hydrocarbon in the presence of hydrogen gas or hydrogen containing hydrogen sulfide, the side reactions of polycondensation and coke formation can be inhibited, and likewise the formation of deposits (coking) in the equipment, especially in the reaction zone, can be prevented, thereby economically, stably and in high efficiency, a A useful lighter oil, from a heavy hydrocarbon, with the additional significant advantage of being able to prevent deterioration of the properties of the lighter oil as well as the high boiling residue. This can be shown particularly in the case of using an atmospheric residue or a vacuum residue of a paraffin-based crude oil such as Minus crude, Taching crude, and the like, known as oils. In particular, these heavy residues are heavy oils considered to be relatively difficult to convert into a lighter and higher value product by phase separation of the product. According to the present invention, by advantageously using the excellent characteristic of the paraffinic properties of these heavy oils, it has become possible to effect their high conversion into a lighter and more valuable product. As a result, the fraction having the low boiling point of the lighter product which is obtained by atmospheric or vacuum distillation can be intended for use directly in steam pyrolysis without going through the hydrotreatment step to give raw materials for the chemistry of oil. As a result, equipment such as hydrotreating equipment is no longer needed, and there is also a strong effect of decreasing the amount of hydrogen consumption. On the other hand, the high boiling point residue removed by distillation can be sufficiently used as a liquid fuel, much like heavy oils obtained directly from the fuel source in the practice of the present process or in boilers in general.

The high boiling fraction removal steps are required to bring a low boiling fraction to the subsequent steam pyrolysis steps or to the hydroprocessing step.

As a method for removing a high boiling fraction, high pressure gas separation, atmospheric distillation or vacuum distillation conventionally used, and additionally solvent deasphalting can be employed. It is also possible to perform a fractionation into a naphtha fraction (lower boiling point of 200 OC), a gas kerosene fraction (boiling point of 200-3430C) and a vacuum gas oil fraction. (boiling point 343-5450C). Various kinds of these lighter fractions can be subjected to steam pyrolysis, as is or after hydrotreatment.

To subject the thermally cracked oil, after removal of the high boiling point fraction, to the hydrotreatment step, the hydrotreatment method described above can be used as it is. However, as the feed oil employed is the thermally cracked oil from which the toxic materials for the catalyst such as asphaltenes or metals have been removed, the catalyst employed has a higher activity due to the fact that the superficial surface. as long as the physical property of the porous support is greater, it is therefore not particularly necessary to increase the volume of the pores to large dimensions as in the case of the catalyst for the treatment of an oil having a high asphaltene content or metals.

The thermally cracked oil from which the high boiling fraction has been separated and removed in the separation step or the hydrotreated oil recovered in the hydrotreatment step can be used as the feed oil dar. s the steam pyrolysis step, and it is also possible to perform the steam pyrolysis of each fractionated fraction separately or as a mixture with other petroleum fractions depending on the desired use.

The steam pyrolysis mode to be used in the steam pyrolysis in the process of the present invention is not particularly limited, but various modes can be employed, and it is also possible to use a tubular heater which has a Existing naphtha cracking heater, as is or with a slight modification.

The reaction conditions in the steam pyrolysis step can be a weight ratio of steam to oil of 0.2 to 2.0, preferably 0.4 to 1.5, pyrolysis temperature 700 to 9000C, preferably 750 to 9000C and a residence time of 0.5 to 2.0 seconds, preferably 0.1 to 0.6 seconds
The product obtained by the steam pyrolysis reaction is taken from the heater to a rapidly cooled heat exchanger for heat recovery, followed by separation and purification, to give gaseous olefins and monocyclic aromatics, fuel oils. by-products and other hydrogen and hydrocarbon by-products.

In the practice of the process according to the invention, the gaseous hydrogen to be used in the thermal cracking stage, and the hydrotreatment stage can be introduced by circulation of the hydrogen gases separated from the respective stages, sometimes after removal of the hydrogen sulfide and ammonia contained therein, and it is generally desirable to supplement the hydrogen gas in an amount corresponding to the hydrogen gas consumed. In this case, a source of hydrogen, the hydrogen gas by-product in the steam pyrolysis, or the hydrogen gas obtained in the vapor modification of the gaseous hydrocarbon by-product or the fuel by-product. product may also be available.

Referring now to the accompanying drawings, embodiments of the process for producing gaseous olefins and monocyclic aromatics using a heavy hydrocarbon as a feedstock will be described in detail.

Figures 1 and 2 show different examples of equipment diagrams for the practice of the production process of gaseous olefins and aromatic products.
monocyclic according to the present invention. Referring to the steps of Figure 1, the feedstock of a heavy hydrocarbon mixed with at least two kinds of substances according to the present invention is raised in pressure by a feed pump to be fed, by a line. 1, and hydrogen gas or gas containing hydrogen sulphide is pressurized by a compressor to be fed from line 2 respectively, to thermal cracking equipment 3, where the heavy hydrocarbon is converted into a light product and of greater value. The lighter product obtained is delivered by a line 4, to be cooled there rapidly, to a gas-liquid separator 5. The high pressure gas-liquid separator generally consists of two stages of a hot separator and a cold separator. The hydrogen-enriched gas at the outlet of the separator is discharged through a line 6 and after raising to a desired pressure, if desired, it is circulated to the thermal cracking equipment 3. The hot separator liquids and cold separator do not necessarily have to be preheated and are fed through a line 7 to an atmospheric rinser Then the atmospheric residue removed through a withdrawal tube 9, at the bottom of the atmospheric rinser 8, is delivered to a vacuum rinser 10 to be there treaty.

The rinser 10 operates under vacuum with the equipment of a vacuum generating device in order to lower the operating temperature, and sometimes it is also possible to use steam distillation as an auxiliary means or steam blown from the bottom of the tank. the tower to lower the partial pressure of the oil. The atmospheric fraction at the outlet of the atmospheric rinser 8 and the vacuum fraction at the outlet of the vacuum rinser 10, after removal of the residual gases via lines 11 and 12 respectively, are mixed by passing through lines 13 and 14 for a introduction into a line 15. On the other hand, the vacuum residue withdrawn through a withdrawal tube 16 at the bottom of the vacuum rinser 10 can be used as it is as a liquid fuel, but it can be introduced into a solids separator 17 for be subjected to the solids separation operation. Separation 17 may include, for example, a centrifugal separator, a filter, solvent sedimentation means, and a combination thereof.
Part of the vacuum residue or the solid or the solid subjected to further cleaning and drying (not shown) can be recycled through line 18 to be added to the heavy hydrocarbon feedstock. The vacuum liquid residue separated from most of the solid in separator 17 is discharged through line 19 and can be used as liquid fuel. The distilled oil introduced into line 15 is elevated in pressure by a feed pump and is applied to hydrotreatment equipment 20 to be hydrotreated therein, the hydrogen gas being elevated in pressure by means of a compressor. The hydrotreated product is cooled to a desired temperature by a heat exchanger, and the like, and is supplied through line 22 to a high pressure gas-liquid separator 23 for gas and liquid separation. The separated hydrogen enriched gas is circulated through a line 24, after raising to a desired pressure if necessary, to the hydrotreatment equipment 20. Furthermore, the hydrotreated liquid product is expanded by passing through a line 25 to be introduced into a gas-liquid separator 26 and after evacuation of the residual gases with a high vapor pressure via a line 27, it is delivered via a line 28 to a steam pyrolysis equipment 29. In this equipment, the hydrotreated product is pyrolyzed
steam and the pyrolyzed product is withdrawn through a line 30, cooled, separated, purified, and recovered in the form of gaseous oelfins, monocyclic aromatics, by-product hydrogen, by-product fuel, etc.

The diagram shown in FIG. 2 represents the case where no hydrotreatment step is required, which corresponds to the diagram shown in FIG. 1 where the symbols 20 to 28 are omitted.

The present invention will be better described below with reference to the following examples which should in no way limit it.

EXAMPLE 1
Using a vacuum residue of Minus crude (100% by weight of a fraction having a boiling point above 5200C) as the feed oil, thermal cracking was carried out by continuous equipment operating at high pressures1 having a reactor formed of a maturation-type vessel 40 mm internal diameter and 100 mm high equipped with a stirrer mounted with three turbine-type blades each having three fins. For the two kinds of components added to the feed oil, nickel octoate in an amount of 200 ppm was added as nickel, based on the feed oil, and carbon black to the medium particle size oil furnace. of 20 mpp by electronic microscope (EM), specific surface area of 120 m 2 / g by the method of BET3 in an amount of 2% by weight based on the feed oil respectively, and the whole was stirred. feed oil before introducing it into the reactor. r.

The reaction conditions employed for the thermal cracking were a temperature of 4950C, a pressure of 200 bar, a residence time (based on the cold liquid) of 2Q minutes and a hydrogen / feed oil ratio of 2000 Nl / L, the number of agitator revolutions being 1000 rpm. The continuous operation time was 100 hours as the steady state operation time.

The products obtained were 5.8% by weight of gas
C1 - C4, 42.5% by weight of the GO fraction by atmospheric distillation (boiling point 3430C,), 29.0% by weight of the VGO fraction by vacuum distillation (boiling point 343 - 520 C) and 20.0% by weight of the residue in vacuo (VR). The content of asphaltenes (defined as insoluble in hexane and soluble in tetrahydrofuran) was 2.1% by weight and the content of cokes (defined as insoluble in tetrahydrofuran and in hexane) was 1.0. % in weight. The amount of hydrogen consumed was 110 Nl per kg of feedstock. The conversion of heavy feed products into a lighter and higher value product defined by the following formula

<tb><SEP> proportion <SEP> of <SEP> the <SEP> fraction <SEP> having nn <SEP> point
<tb><SEP> of boiling <SEP> greater <SEP> than <SEP> 5200C <SEP> in <SEP> on
<tb><SEP> product
<tb> 1 <SEP> ^ <SEP> x100 <SEP>
<tb><SEP> proportion <SEP> of <SEP> the <SEP> fraction <SEP> having <SEP> a <SEP> point
<tb><SEP> of boiling <SEP> greater <SEP> than <SEP> 5200C <SEP> in <SEP> the
<tb><SEP> load <SEP> power
<tb> was found to be 80% by weight. The yield of the liquid fraction converted to an upper product of boiling point below 5200C was 74.2% by weight as the sum of GO and VGO.

In addition, the amount of coking (amount of deposit) on the inner wall surface of the reactor after 100 hours of steady state operation was extremely low, 40 ppm based on the total weight of the reactor. feed oil.

COMPARISON EXAMPLE N 1
Example 1 was repeated except that the two kinds of components were not added to the feed oil. As a result, about two hours after the start of operation, the reactor was completely plugged with coke, so stable operation could not be achieved. Under the conditions where stable operation was possible, the yield of the liquid fraction having a boiling point below 5200C was less than 34.1% by weight, more than half the yield of Example 1.

COMPARISON EXAMPLE N02
Example 1 was repeated except that no ultra-fine particle was added and only nickel octoate was added in an amount of 500 ppm as nickel. As a result, about 4 hours after the start of operation, the reactor was completely plugged with coke. The yield of the liquid fraction having a boiling point below 5200C was 75% by weight, but the amount of coke formed was 3.5% by weight and the major part of it, that is - that is, about 3.0% by weight was found to participate in the coking of the reactor.

COMPARISON EXAMPLE N 3
The exercise was repeated: .ple 1 except that the gold did not add a transition metal corrosive and that only dt black from the oil fcyer smoke was added in an amount of 4% in weight. As a result, about 15 hours after the start of operation, the reactor was completely clogged with coke. The yield of the liquid fraction having a boiling point below 5200C was 74% by weight, but the amount of coke formed reached 6.1% by weight, the amount of coke in the reactor being about 0.8%. in weight.

COMPARISON EXAMPLE N 4
Example 1 was repeated except that 3% by weight of diluted and pulverized coke standardized to have a particle size of between about 10 and 60 was used instead of carbon black. As a result, about 3 hours after the start of operation, the reactor was completely clogged with coke. The yield of liquid fractions having a boiling point below 5200C was 73% by weight but the amount of coke formed was 3.1% by weight, of which about 2.2% by weight was found to have undergone coking with the diluted and pulverized coke added to the reactor.

COMPARISON EXAMPLE N05
Example 1 was repeated except that 3% by weight of a nickel-tungsten catalyst supported on porous alumina e having a specific surface area of 220 m2 / g (metho @ e) was used. of BET) containing 4% by weight of nickel oxide and 15% by weight of tungsten oxide, pulverized to particle sizes of 60y4 or less, instead of nickel octoate and carbon black. , after operation for about 7 hours the reactor was completely blocked and it was not possible to continue stable operation. The yield of the liquid fraction having a boiling point below 520 C was; 72 wt% and the amount of coke formed was 1.8 wt%, but in the reactor it was found that about 1.296 wt% coke had been coked in a form partially containing the added catalyst.

COMPARISON EXAMPLE 6
Example 1 was repeated except that an aqueous solution of ammonium molybdenate dissolved in water, in an amount of 500 ppm as molybdenum, was added to the feed oil for to form an emulsion, to which was added 3% by weight of pulverized particles of about 10 to 30 of a complex oxide of silica-alumina (silica 60%, alumina 40%) which was a porous material having a specific surface area of 400 m2 / g (BET method) instead of nickel octoate and carbon black.

As a result, after operating for about 10 hours, the reactor was completely plugged and stable operation could be continued. The yield of the liquid fraction having a boiling point below 5200 C was 75% by weight and the amount of coke formed was 3.5% by weight, but in the reactor it was found that about 1, 2% by weight of the coke had been coked in the form partially containing the added particulate matter.

As can be seen from the results of Example 1 and Comparative Examples 1 to 6, the present invention can be regarded as being excellent for obtaining a high yield of lighter oil by cracking a heavy hydrocarbon. On the other hand, the residual oil having a boiling point above 5200C which is obtained in the present invention has a viscosity of only 22 cst at 1500C, and its combustibility by thermogravimetric analysis is similar to the vacuum residue of crude from Minus as a feedstock, and thus it can be used as fuel.

EXAMPLE 2 - 10
Using a vacuum residue of Minus crude (100% of the fraction having a boiling point above 5200C) as the feed oil, various combinations of two kinds of components were added thereto in predetermined amounts as mentioned above. afterwards to carry out the thermal cracking by the same reaction device as that used in Example 1.

In fact, in the case of Example 2, vanadium octoate was added in an amount of 300 ppm in the form of vanadium and carbon black in the tunnel mean particle size: 14 m (EM method), specific surface area: 300 m2 / g (BET method)) was added thereto in an amount of 2% by weight, respectively.

In the case of Example 3, copper octoate was added in an amount of 500 ppm in the form of copper and silicas produced by a liquid phase process [mean particle size: 20 m (method
EM), specific surface area: 150 m2 / g (BET method) 3 were added thereto in an amount of 2% by weight, respectively.

In the case of Example 4, molybdenum naphthenate was added in an amount of 100 ppm, in the form of molybdenum and silicas produced by vapor phase processes [average particle size: 8 m (EM method), specific surface area: 350 m2 / g (BET method)} was added thereto in an amount of 1% by weight, respectively.

In the case of Example 5, an aqueous solution of ammonium heptatungstate was added in an amount of 600 ppm in the form of tungsten and alumina produced by a vapor phase process Average particle size: 20 mS (EM method), specific surface area: 100 m2 / g (BET method) 3 was added thereto in an amount of 3% by weight, respectively.

In the case of Example 6, an aqueous solution of cobalt sulfate in an amount of 800 ppm, as cobalt, and an anatase-type titanium oxide produced by a medium particle size vapor phase process were added. : 30 mS (EM method), specific surface area: 50 m2 / g (BET method) was added in an amount of 68 by weight, respectively.

In the case of Example 7, nickel stearate was added in an amount of 300 ppm in the form of nickel and calcined coke micropulverized by a jet mill mean particle size: 400 m (EM method), surface area Specific: 35 m2 / g (BET method) was added thereto in an amount of 10% by weight, respectively.

In the case of Example 8, chromium resinate was added in an amount of 700 ppm in the form of chromium and carbon black by thermal decomposition Average particle size: 180 m (EM method), specific surface area: 15 m2 / g (BET method) J was added in an amount of 7% by weight, respectively.

In the case of Example 9, nickel acetylacetonate was added in an amount of 500 ppm in the form of nickel and fluid coke micropulverized by a jet mill average particle size: 800 mlV (EM method), specific surface area: 25 m2 / g (BETJ method was added in an amount of 10% by weight, respectively.

In the case of Example 10, pentacarbonyl-iron was added in an amount of 1000 ppm as iron and silicates produced by liquid phase processes (containing 18% calcium oxide) average particle size : 30 m (EM method) specific surface area: 80 m 2 / g (BET method)] were added in an amount of 3% by weight, respectively.

In Examples 7 and 9, 1% by weight of a dispersing agent composed mainly of petroleum calcium sulfonate and a dispersing agent mainly composed of polybutenylsuccinimide were added to the feed oil, respectively.

The reaction conditions employed for the thermal cracking were a temperature of 4950C, a pressure of 200 bar, a residence time (based on cold liquid) of 20 minutes, and a stirrer revolutions of 1000 rpm in all examples 2 to 10, a ratio of hydrogen to feed oil of 2000 Nl / l in examples 2 to 7 and a ratio of hydrogen with 3 mole% hydrogen sulfide to oil 2000 Nl / l feed to Examples 8-10. Steady state operation for each example was 30 hours.

As a result of experience, in all these examples, stable operation was possible without the reactor becoming blocked, the conversion being between 75 and 858 by weight and the yield of the liquid fraction boiling at less than 520 C being between 70 and 78% by weight. In addition, the amount of coke formed was between 0.7 and 2% by weight, and the amount of coking on the inner wall surface of the reactor was between 40 and 200 ppm based on the total weight of the feedstock. power supply.

EXAMPLE II
Lightweight Arabian vacuum oil (boiling point 343 - 5200C) containing 1000 ppm, in the form of nickel, nickel stearate and 10% by weight of a carbon black in the fuel oil stove Average particle size: 15 ms (EM method), specific surface area 200 m2 / gJ was introduced in an amount of 3 kg into an autoclave with an internal volume of 10 liters, hydrogen gas containing 5 mol% of hydrogen sulphide was pressurized in the autoclave to a loading pressure of 100 bar and the reaction was carried out with stirring at 1000 rpm at a temperature of 4200C for one hour. After the reaction, the contents were filtered, washed and extracted with tetrahydrofuran, followed by drying to obtain a solid product.

The solid product was added to a vacuum residue of crude de Minus dissolved by heating (100% by weight of
the fraction having a boiling point above 5200C)
up to 10% by weight content and was dispersed by ultrasonic wave. The resulting dip was added to the same Minus vacuum residue as above to a solid content of 2% by weight.

The mixture was stirred well and used in the
stable operation of the reaction undertaken by the same device and under the same conditions as
Example 1 for 30 hours.

As a result of the experiment, it was possible to carry out the operation in a stable manner without plugging the reactor, the conversion being 81.6% by weight and the yield of the liquid fraction obtained having a boiling point below 5200C being 75 , 6% by weight.

The amount of coke formed was 0.8% by weight and the amount of coking on the inner wall surface of the reactor was 40 ppm based on the total weight of the feedstock.

EXAMPLE 12
Silicas produced by vapor phase processes Average particle size: 16 mP (method
EM), specific surface area: 200 m2 / g (BET method) 3 (300 g) were suspended in hydrogen gas containing 5 mol% of hydrogen sulfide in a fluidized bed and, while allowing them to fly with rotation in the gas stream, they were subjected to a mixture by atomization with a
aqueous solution of ammonium heptamolybdate in an amount of 15 g in the form of molybdenum. So everything
maintaining the temperature of the gas stream at 4300C,
the reaction was carried out for one hour.
solid obtained by this process was added to the residue
under Minus crude vacuum (100% by weight of the fraction having
a boiling point above 5200C) to a content of 2% by weight, and the feed oil was completely stirred and supplied to the reactor. The reaction device and reaction conditions were the same as Example 1, and steady state operation was undertaken for 20 hours.

As a result of the experiment, the operation could be carried out stably without plugging the reactor, the conversion being 80.9% by weight and the yield of the liquid fraction obtained having a boiling point below 5200C being 74.9% by weight. The amount of coke formed was 1.2 by weight and the amount of coking on the inner wall surface of the reactor was 95 ppm based on the total weight of the feedstock.

EXAMPLE 13
The produced oil obtained in Example 1 was subjected to atmospheric distillation and vacuum distillation to remove the fraction boiling below 5200C. The resulting residue was filtered with heating. The solid residue after extracting the filtered product with tetrahydrofuran was dried and added to a vacuum residue of Minus crude (100% by weight of the fraction having a boiling point above 5200C) up to 4% by weight , followed by the addition of 0.5% by weight of a dispersing agent composed mainly of calcium petroleum sulfonate. The mixture was stirred well and introduced into the reactor. The device and reaction conditions were the same as in Example 1 and steady state operation was undertaken for 30 hours.

As a result of the experiment, the operation could be carried out stably without plugging the reactor, the conversion being 81w88 by weight and the yield of the liquid fraction obtained having a boiling point below 5200C being 75.4. % in weight. The amount of coke formed was 16% by weight and the amount of coking on the inner wall surface of the reactor was 140 ppm based on the total weight of the feedstock.

EXAMPLE 14
The product oil obtained in Example 1 was subjected to atmospheric distillation and vacuum distillation to remove the fraction having a boiling point below 5200 C. The resulting residue was added to a vacuum residue of Minus crude (100% by weight of the fraction having a boiling point above 5200C) up to 4% by weight, followed by addition of molybdenum naphthenate in an amount of 500 ppm as molybdenum based on feed oil and additionally 0.5% by weight of silicas produced by vapor phase processes (average particle size: 8ms (EM method), specific surface area: 350m2 / g (BET method) in the feed oil. The mixture was stirred well and introduced into the reactor. The device and the reaction conditions were as in Example 1, and steady state operation was been undertaken for 30 hours.

As a result of the experiment, the operation could be carried out stably without plugging the reactor, the conversion being 74.8% and the yield of the liquid fraction obtained having a boiling point below 5200C being 69. , 7% by weight. The amount of coke formed was 2.0% by weight and the amount of coking on the inner wall surface of the reactor was 180 ppm based on the total weight of the feedstock.

EXAMPLE 15
Using a vacuum residue of crude Taching (100% by weight of the fraction having a boiling point above 5200C) as the feed oil, thermal cracking was carried out by the same continuous type equipment operating at high temperature. high pressures, than that used in Example 1.

As components to be added to the feed oil were added copper naphthenate in an amount of 500 ppm as copper and silica produced by liquid phase processes mean particle size: 15 m (EM method ), specific surface area: 210m2 / g (BET method) 0 was added up to a content of 2% by weight. The feed was stirred well before it was introduced into the reactor.

The reaction conditions employed for the thermal cracking were a temperature of 4900C, a pressure of 150-bar, a residence time (based on cold liquid) of 20 minutes, and a hydrogen to oil ratio. feed of 2000 Nl / l, the number of agitator revolutions being 1000 rpm. Steady state operation was continuous for 50 hours.

As a result of the experiment, the operation could be carried out stably without plugging the reactor, the conversion being 81.48 by weight and the yield of the obtained liquid fraction having a boiling point below 5200C being 76. , 0% by weight.

The amount of coke formed was 1.4 by weight and the amount of coking on the inner wall surface of the reactor was 20 ppm based on the total weight of the feedstock. The amount of hydrogen consumed was found to be 100 Nl / kg-feedstock.

EXAMPLE 16
Using a vacuum residue of Arabian light crude (100% by weight of the fraction having a boiling point above 5200C) as the feed oil, thermal cracking was undertaken by the same continuous type equipment, operating at high pre-ssions, than that used in Example 1.

For the components to be added to the feed oil, vanadium acetylacetonate was added in an amount of 500 ppm as vanadium and the silica produced by vapor phase processes C mean particle size: 12 mA (EM method), specific surface area: 230 m2 / g (BET method) j was added up to 3% by weight. The feed was stirred well before it was introduced into the reactor.

The reaction conditions employed for the thermal cracking were a temperature of 480 C, a pressure of 200 bar, a residence time (based on the cold liquid of 25 minutes and a hydrogen to feed oil ratio of 2000 Nl / 1, the number of agitator revolutions being 1000 rpm.

Steady state operation was continued for 100 hours.

As a result of the experiment, the operation could be carried out stably without plugging the reactor, the conversion being 74.7% by weight and the yield of the liquid fraction obtained having a boiling point below 5200C being 68.9% by weight. The amount of coke formed was 1.0% by weight and the amount of coking on the inner wall surface of the reactor was 200 ppm based on the total weight of the feedstock. The amount of hydrogen consumed was found to be 170 Nl / l kg-feedstock.

EXAMPLE 17
Using a vacuum residue of crude from
Venezuela (100% by weight of the fraction having a boiling point above 5200C) as the feed oil, thermal cracking was carried out by the same equipment of the continuous type, operating at high pressures, as that used for example. 1.

For the components to be added to the feed oil, nickel naphthenate was added in an amount of 500 ppm as nickel and silica produced by the liquid phase processes. Average particle size: 15 m2 '( EM method), specific surface area: 210 m2 / g (BET method)] was added up to a content of 2% by weight. The feed was stirred well before it was introduced into the reactor.

The reaction conditions employed for the thermal cracking were a temperature of 4850C, a pressure of 200 bar ^, a residence time (based on cold liquid) of 25 minutes, and a ratio of hydrogen to feed oil. 2000 Nl / l, the number of agitator revolutions being 1000 rpm.

Steady state operation was continued for 20 hours.

As a result of the experiment, the operation could be carried out stably without plugging the reactor, the conversion being 78.2% by weight and the yield of the liquid fraction obtained having a boiling point below 5200C being 71 , 9% by weight. The amount of coke formed was 2.8% by weight and the amount of coking on the inner wall surface of the reactor was 240 ppm based on the total weight of the feedstock. The amount of hydrogen consumed was found to be 190 Nl / kg-feedstock.

EXAMPLE 18
Using a Maya crude vacuum residue
(100% by weight of the fraction having a boiling point above 5200C) as feed oil, thermal cracking was undertaken by the same equipment of the continuous type operating at high pressures as that used in Example 1 .

For the components to be added to the feed oil, nickel naphthenate was added in an amount of 500 ppm as nickel and additionally silica produced by liquid phase processes average particle size: 15 mzC / (EM method), specific surface area: 210 m2 / g (BET method) 0 has been added up to 2% by weight. The feed was stirred well before it was introduced into the reactor.

The reaction conditions employed for the thermal cracking were a temperature of 4850C, a pressure of 200 bar, a residence time (based on cold liquid) of 25 minutes, and a hydrogen to oil feed ratio of. 2000 Nl / l, the number of agitator revolutions being 1000 rpm.

Steady state operation was continued for 20 hours.

As a result of the experiment, the operation could be carried out stably without plugging the reactor, the conversion being 75.4% by weight and the yield of the liquid fraction obtained having a boiling point below 5200C being 68. , 1% by weight. The amount of coke formed was 2.7 wt% and the amount of coking on the inner wall surface of the reactor was 280 ppm based on the total weight of the feedstock. The amount of hydrogen consumed was found to be 220 Nl / kg-feedstock.

EXAMPLE 19
A mixture of all the oils produced in Examples 1 to 5 and 10 to 14 was used as the feed oil. By a continuous type hydrotreating reaction device with an internal diameter of 18 mm, the bed reactor was used. stationary was packed with a Ni / Mo / Al catalyst having a surface area of 270 m2 / g and a porosity of 0.75 ml / g containing 5 wt% nickel oxide and 20 wt% oxide of molybdenum, after application of a presulfurization of the catalyst, the hydrogenation was carried out under the reaction conditions of a ratio of hydrogen to the feed oil of 1000 Nl / l, a temperature of 4000C , a pressure of 180 bars, and
0.8h -1 LHSV. The properties of the feed oil and the recovered hydrotreated oil are shown in Table 1.

EXAMPLE 20
Using a fraction obtained by removing the high-boiling components having a boiling point above 5200C, from the oil produced in Example 1 by atmospheric distillation and vacuum distillation, as the feed oil, and a Co-Mo / Al catalyst having a surface area of 240 m2 / g and a porosity of 0.53 ml / g containing 4% by weight of cobalt oxide and 142 by weight of molybdenum dioxide, applied with presulfurization, a hydrotreatment was carried out by the same hydrotreatment reaction device of the continuous type as that used in Example 19 at the reaction conditions of a hydrogen to feed oil ratio of 1000 Nl / l, at a temperature of 3900C, a pressure of 150 bar and an LHSV of 1.0 h -1. The properties of the feed oil and the recovered hydrotreated oil are shown in Table 1.

EXAMPLE 21
Using a fraction obtained by removing the high-boiling components having a boiling point greater than 520DC from the product of Example 16 by atmospheric and vacuum distillation, as a feed oil, and a Ni-Mo / Al catalyst having a surface area of 230 m2 / g and a porosity of 0.60 m / g containing 4% by weight of nickel oxide and 14% by weight of molybdenum oxide, with presulfurization, a hydrotreatment was carried out by the same continuous type hydrotreatment reaction device as that used in Example 19 under the reaction conditions of a hydrogen to feed oil ratio of 1000 Nl / l, a temperature of 4000C, a pressure of 200 bars and LHSV of 0.8 H 1 The properties of the feed oil and of the recovered hydrotreated oil are shown in Table 1.

TABLE 1 Changes in oil properties by
hydrotreatment

<tb><SEP> Example <SEP> 19 <SEP> Example <SEP> 20 <SEP> Example <SEP> 21
<tb> Char- <SEP> oil <SEP> Charge <SEP> oil <SEP> Charge <SEP> oil
<tb><SEP> ge <SEP> hydro- <SEP> from ali- <SEP> hydro- <SEP> from ali- <SEP> hydro
<tb><SEP> ali- <SEP> trai- <SEP> menta- <SEP> processed <SEP> menta- <SEP> processed
<tb><SEP> menta- <SEP> tée <SEP> tion <SEP> tion
<tb><SEP> tion
<tb> Density <SEP> (15/4 C) <SEP> 0.8490 <SEP> 0.8100 <SEP> 0.832 <SEP> 0.8048 <SEP> 0.8703 <SEP> 0.8358
<tb> H / C <SEP> (atomic <SEP> ratio) <SEP> 1.79 <SEP> 1.95 <SEP> 1.88 <SEP> 1.99 <SEP> 1.69 <SEP> 1 , 92
<tb><SEP> content in <SEP> sulfur <SEP> (% <SEP> in
<tb> weight) <SEP> 0.05 <SEP> traces <SEP> 0.02 <SEP> traces <SEP> 2.31 <SEP> 0.01
<tb><SEP> content in <SEP> nitrogen
<tb><SEP> (% <SEP> in <SEP> weight) <SEP> 0.12 <SEP> 0.05 <SEP> 0.05 <SEP> 0.02 <SEP> 0.06 <SEP> 0.01
<tb> Carbon <SEP> residue <SEP>
<tb> deCbnradson <SEP> (% <SEP> in <SEP> weight <SEP> 6.40 <SEP> 0.02 <SEP> 0.07 <SEP> traces <SEP> 0.15 <SEP> traces
<tb><SEP> Type <SEP> of analysis
<tb><SEP>(<SEP> chromatography in
<tb><SEP> column)
<tb> Component <SEP> saturated <SEP> (%
<tb><SEP> enweight) <SEP> 75.0 <SEP> 91.5 <SEP> 79.3 <SEP> 93.0 <SEP> 55.2 <SEP> 91.1
<tb><SEP> aromatic component
<tb><SEP> (% <SEP> in <SEP> in <SEP> weight) <SEP> 18.9 <SEP> 8.3 <SEP> 15.7 <SEP> 6.9 <SEP> 39, 4 <SEP> | <SEP> 8.4
<tb> Polar <SEP> components
<tb><SEP> (% <SEP> in <SEP> weight) <SEP> 6.1 <SEP> 0.2 <SEP> 5.0 <SEP> 0.1 <SEP> 5.4 <SEP> 0.5
<tb> Distribution <SEP> of hydro
<tb> gene <SEP> (H-RMN)
<tb><SEP> hydrogen <SEP> aromatic <SEP> 3.9 <SEP> 1.1 <SEP> 3.2 <SEP> 1.0 <SEP> 6.1 <SEP> 1.3
<tb><SEP> (%)
<tb><SEP> hydrogen <SEP> Olefinic <SEP> 1.1 <SEP> traces <SEP> 1.0 <SEP> traces <SEP> 1.4 <SEP> traces
<tb><SEP> (%)
<tb><SEP> hydrogen <SEP> aromatic <SEP> 6.0 <SEP> 4.8 <SEP> 5.8 <SEP> 4.8 <SEP> 12.8 <SEP> 7.2
<tb><SEP> in <SEP> position &alpha;; (%)
<tb><SEP> hydrogen <SEP> Methylene <SEP> (%) <SEP> 66.4 <SEP> 69.3 <SEP> 65.8 <SEP> 69.5 <SEP> 55.5 <SEP> 66.4
<tb><SEP> hydrogen <SEP> from <SEP> methyl
<tb><SEP> (%) <SEP> 22.6 <SEP> 25.0 <SEP> 24.2 <SEP> 24.7 <SEP> 24.2 <SEP> 25.1
<tb>
EXAMPLE 22
The high-boiling components having a boiling point above 5200C were removed, by atmospheric vacuum distillation, from the thermally cracked product removed from the gaseous components obtained in Example 1 using the vacuum residue of crude. of Minus as a feedstock.

The fraction boiling at less than 5200C was pyrolyzed with steam by a pyrolyzer of the tubular reheater type under conditions of an inlet temperature of 5500C, an outlet temperature of 8300C and an outlet pressure of 0, 8 bar, with a steam to oil weight ratio of 1.0 and a residence time of 0.2 seconds to obtain olefins and monocyclic aromatics.

The results of the steam pyrolysis are given as well as the yields of the main chemical raw materials (gaseous and aromatic olefins. Main monocyclic) per feedstock of the vacuum residue of Minus crude in Table 2.

EXAMPLE 23
The hydrotreated oil removed from the gas components obtained in Example 20 using the vacuum residue of Minus as raw material was subjected to steam pyrolysis as in Example 22 under the conditions of an inlet temperature of. 5500C, an outlet temperature of 8300C, an outlet pressure of 0.8 bar, a steam to hydrotreated oil weight ratio of 1.0 and a residence time of 0.2 second to obtain olefins and monocyclic aromatics.

The results of the steam pyrolysis are given together with the yields of the main chemical raw materials (gaseous olefins and main monocyclic aromatics), by feedstock, in Table 2.

COMPARISON EXAMPLE 7
The thermally cracked product obtained during the stable operation of Comparative Example No. 1, from which the gaseous components had been removed, was subjected to atmospheric and vacuum distillation in the separation step, - and to the fraction boiling below 5200C, the process of the hydrotreatment step and the steam pyrolysis step were applied as in Examples 20 and 23, respectively.

The results of the steam pyrolysis are shown, along with the yields of the main chemicals (gaseous olefins and main monocyclic aromatics) in Table 2.

COMPARISON EXAMPLE N 8
The thermal cracking step was carried out using a vacuum residue of Minus crude as a feed oil, the same hydrotreater as in Example 19, a 70% Ni-W catalyst. weight of silica / 30% by weight of alumina with a surface area of 230 m2 / g and a porosity of 0.37 ml / g containing 6% by weight of nickel oxide and 19% by weight of tungsten oxide , and also by employing the conditions in which the deterioration of the activity of the catalyst is not noticed at the start of operation, i.e. a temperature of 3800C, a reaction pressure of 200 bar, LHSV 0.5 h 1 and a hydrogen / feed oil ratio of 2000 Nl / l. The yield of the liquid fraction boiling at less than 5200C was only 16.5% by weight. The resulting liquid fraction was subjected to the same steam pyrolysis as in Example 22. The results of the steam pyrolysis are given as well as the yields of the main chemical materials (gaseous olefins and main monocyclic aromatics) for the feed. power supply, in Table 2.

As can be seen from the results of Examples 22 and 23 and Comparative Examples Nos. 7 and 8, the process of the present invention is excellent for the decomposition of heavy hydrocarbons to provide raw materials for steam pyrolysis, offering thus high yields of petrochemical raw materials.

EXAMPLE 24
From the thermally cracked product removed from the gaseous components obtained in Example 15 using the vacuum residue of Taching crude as a feedstock, the high-boiling components having a higher boiling point were removed. at 5200C, according to atmospheric and vacuum distillation.

The fraction boiling below 52O0C was pyrolyzed with steam by a pyrolyzer of the tubular heater type at the conditions of an inlet temperature of 55O0C, an outlet temperature of 83O0C, an outlet pressure of 0 , 8 bar, a weight ratio of steam to oil of 1.0 and a residence time of 0.2 seconds to obtain olefins and monocyclic aromatics.

The results of the steam pyrolysis are given, along with the yields of the main chemical raw materials (main gaseous olefins and monocyclic aromatics), by feedstock, in Table 2.

EXAMPLE 25
From the thermally cracked product removed from the gaseous components obtained in Example 16 using the vacuum residue of Arabian light crude as a feedstock, the high boiling components having a boiling point greater than 52O0C have were removed by separation by atmospheric distillation and under vacuum.

The fraction boiling at less than 52O0C was pyrolyzed with steam by a pyrolyzer of the tubular heater type at the cDnslitions of an inlet temperature of 5500C, outlet temperature of 8300C, outlet pressure zone of 0.8 bar, d A steam to oil weight ratio of 1.0 and a residence time of 0.2 seconds to obtain olefins and monocyclic aromatics.

The results of the steam pyrolysis are given together with the yields of the main chemical raw materials (gaseous olefins and aromatics-monocyclic main), by feedstock, in Table 2.

EXAMPLE 26
The hydrotreated oil removed from the gas components obtained in Example 21 using the vacuum residue of Arabian light crude as a feedstock was steam pyrolyzed by a tubular heater type pyrolyzer at temperature conditions. inlet of 5500C, an outlet temperature of 83O0C, an outlet pressure of 0.8 bar, a vapor / hydrogenated oil weight ratio of 1.0 and a residence time of 0, 2 seconds to obtain olefins and monocyclic aromatics.

The results of the final step of subjecting the hydrogenated oil to steam pyrolysis are given as well as the yields of the main chemical raw materials (gaseous olefins and main monocyclic aromatics) per feedstock in Table 2.

Table 2 Steam Pyrolysis Results and Yields of Major Chemical Raw Materials by Feedstock

Example <SEP> Example <SEP> Example <SEP> of <SEP> Example <SEP> of <SEP> Example <SEP> Example <SEP> Example
<tb> 22 <SEP> 23 <SEP> comparai- <SEP> comparai- <SEP> 24 <SEP> 25 <SEP> 26
<tb> sound <SEP> n <SEP> 7 <SEP> sound <SEP> n <SEP> 8
<tb> Hydrogen <SEP> 0.7 <SEP> 0.8 <SEP> 0.8 <SEP> 0.7 <SEP> 0.7 <SEP> 0.7 <SEP> 0.9
<tb> Methane <SEP> 10.4 <SEP> 10.6 <SEP> 10.6 <SEP> 9.1 <SEP> 9.7 <SEP> 9.0 <SEP> 11.0
<tb> Yield <SEP> Ethylene <SEP> 28.1 <SEP> 32.0 <SEP> 30.8 <SEP> 31.2 <SEP> 29.2 <SEP> 23.0 <SEP> 28.9
<tb> of
<tb> Propylene <SEP> 14.2 <SEP> 15.8 <SEP> 15.1 <SEP> 15.5 <SEP> 13.8 <SEP> 10.7 <SEP> 14.1
<tb> products
Main <tb><SEP> Butadiene <SEP> 5.1 <SEP> 7.4 <SEP> 6.8 <SEP> 7.0 <SEP> 6.1 <SEP> 5.0 <SEP> 7.2
<tb> (% <SEP> in
<tb> Aromatics <SEP> monocyclic
<tb> weight)
<tb> (C6 <SEP> to <SEP> C8 <SEP>) <SEP> 11.1 <SEP> 12.4 <SEP> 9.8 <SEP> 13.2 <SEP> 10.2 <SEP> 8.6 <SEP> 14.7
<tb> Cracked <SEP> Essence
<tb> (C5 <SEP> - <SEP> 200 C) <SEP> 17.3 <SEP> 19.7 <SEP> 18.8 <SEP> 20.1 <SEP> 16.6 <SEP> 13, 8 <SEP> 21.7
<tb> Heavy <SEP> oil, <SEP> (plus <SEP> of
<tb> 200 C) <SEP> 16.9 <SEP> 6.2 <SEP> 7.1 <SEP> 5.8 <SEP> 15.8 <SEP> 32.3 <SEP> 8.2
<tb> Yield <SEP> of <SEP> raw materials <SEP> chemical <SEP>
<tb> main <SEP> (% <SEP> in <SEP> weight) <SEP> (1) <SEP> 58.5 <SEP> 67.6 <SEP> 62.5 <SEP> 66.9 <SEP > 59.3 <SEP> 47.3 <SEP> 64.9
<tb> CONTINUED FROM TABLE 2

example <SEP> example <SEP> ex. of <SEP> ex. of <SEP> example <SEP> ex. <SEP> eg.
<tb>

22 <SEP> 23 <SEP> comp.7 <SEP> comp.8 <SEP> 24 <SEP> 25 <SEP> 26
<tb> Yield <SEP> of <SEP> oil <SEP> thermally
<tb> cracked <SEP> boiling <SEP> to <SEP> minus <SEP> of <SEP> 520 C
<tb> 74.2 <SEP> 74.2 <SEP> 34.1 <SEP> 16.5 <SEP> 76.0 <SEP> 68.9 <SEP> 68.9
<tb> in <SEP> step <SEP> of <SEP> thermal <SEP> cracking
<tb><SEP>%<SEP> in <SEP> weight <SEP> (2)
<tb> Yield <SEP> of <SEP> hydrotreated oil <SEP>
<tb> in <SEP> the <SEP> hydrotreatment step
<tb> (% <SEP> in <SEP> weight) <SEP> (3) <SEP> - <SEP> 99.3 <SEP> 99.5 <SEP> - <SEP> - <SEP> - <SEP > 99.0
<tb> Yield <SEP> of <SEP> raw materials <SEP>
<tb> chemical <SEP> main <SEP> by <SEP> load
<tb> power supply <SEP> (% <SEP> in <SEP> weight) <SEP> (4) <SEP> 43.4 <SEP> 49.8 <SEP> 21.2 <SEP> 11.0 <SEP> 45.1 <SEP> 32.6 <SEP> 44.3
<tb> Note 1) Yield of main chemical raw materials = Yield of ethylene +
Yield of propylene + yield of butadiene + monocyclic aromatics (C6 to C8) 4) Yield of main chemical raw materials per feedstock = (1) X (2) X (3).

EXAMPLES 27 - 30
As a hydrocarbon oil converted to lighter products in the respective thermal cracking stages, it is employed.
the thermally cracked product obtained in Example 11, from which the gaseous components have been removed, in the case of Example 27,
the thermally cracked product obtained in Example 12, from which the gaseous components have been removed, in the case of Example 28,
the thermally cracked product obtained in Example 13, from which the gaseous components have been removed, in the case of Example 29,
the thermally cracked product obtained in Example 14, from which the gaseous components have been removed, in the case of Example 30,
and each oil was subjected to atmospheric and vacuum distillations in the respective separation steps for the removal of components having a boiling point above 5200C.

Each of the hydrocarbon oils extracted from the high boiling point components having a boiling point above 52O0C was subjected to a hydrotreatment as in Example 20.

Each hydrotreated oil removed from the gas components was subjected to steam pyrolysis as in Example 22.

The results of the steam pyrolysis are given, along with the yields of main chemical raw materials (gaseous olefins and main monocyclic aromatics), per vacuum residue of Minus crude, which is the raw material in Table 3. Table 3 Steam Pyrolysis Results and Yields of Major Chemical Raw Materials by Feedstock

Example <SEP> 27 <SEP> Example <SEP> 28 <SEP> Example <SEP> 29 <SEP> Example <SEP> 30
<tb> Hydrogen <SEP> 0.7 <SEP> 0.7 <SEP> 0.8 <SEP> 0.8
<tb> Methane <SEP> 10.0 <SEP> 9.6 <SEP> 10.8 <SEP> 9.9
<tb> Yields <SEP> Ethylene <SEP> 33.2 <SEP> 33.8 <SEP> 31.0 <SEP> 32.1
<tb> of the <SEP> pro
Propylene <SEP> 16.2 <SEP> 16.1 <SEP> 15.2 <SEP> 16.0
<tb> duits
<tb> main- <SEP> Butadiene <SEP> 7.8 <SEP> 7.8 <SEP> 7.9 <SEP> 7.5
<tb> paux <SEP> (%
<tb> Aromatics <SEP> monocyclic <SEP> (C6 <SEP> - <SEP> C8) <SEP> 10.5 <SEP> 10.3 <SEP> 12.7 <SEP> 11.8
<tb> in <SEP> weight)
<tb> Cracked <SEP> gasoline <SEP> (C5 <SEP> - <SEP> 200 C) <SEP> 17.9 <SEP> 16.6 <SEP> 18.5 <SEP> 19.3
<tb> Heavy <SEP> oil <SEP> (plus <SEP> of <SEP> 200 C) <SEP> 7.5 <SEP> 6.5 <SEP> 8.0 <SEP> 7.7
<tb> Yield <SEP> of <SEP> raw materials <SEP> chemical <SEP> main
<tb> (% <SEP> in <SEP> weight) <SEP> (1) <SEP> 67.7 <SEP> 68.0 <SEP> 66.8 <SEP> 67.4
<tb> CONTINUED FROM TABLE 3

example <SEP> example <SEP> example <SEP> example
<tb> 27 <SEP> 28 <SEP> 29 <SEP> 30
<tb> Yield <SEP> of <SEP> thermally <SEP><SEP> cracked <SEP> boiling oil
<tb> to <SEP> minus <SEP> of <SEP> 520 C <SEP> in <SEP> step <SEP> of <SEP> cracking <SEP> thermal <SEP> 75.6 <SEP> 74, 9 <SEP> 75.4 <SEP> 69.7
<tb><SEP>%<SEP> in <SEP> weight <SEP> (2)
<tb> Yield <SEP> of <SEP> hydrotreated oil <SEP><SEP> in <SEP> stage
<tb> hydrotreatment <SEP> (% <SEP> in <SEP> weight) <SEP> (3) <SEP> 99.4 <SEP> 99.3 <SEP> 99.2 <SEP> 99.4
<tb> Yield <SEP> of <SEP> raw materials <SEP> chemical <SEP>
<tb> main <SEP> by <SEP> load <SEP> power supply
<tb> (% <SEP> in <SEP> weight) <SEP> (4) <SEP> 50.9 <SEP> 50.6 <SEP> 50.0 <SEP> 46.7
<tb> Note 1) Yield of main chemical raw materials = Yield of ethylene +
Yield of propylene + yield of butadiene + monocyclic aromatics (C6 to C8) 4) Yield of main chemical raw materials per feedstock = (1) X (2) X (3).

EXAMPLES 31 and 32
Using an atmospheric residue of crude Minus (100% by weight of fraction having a boiling point above 3430C, 45% by weight of fraction having a boiling point above 5200C), as feed, we have carried out thermal cracking by the same equipment of the continuous type, operating at high pressures, as in Example 1.

For both kinds of components to be added to the feed oil in thermal cracking, molybdenum naphthenate in an amount of 100 ppm was added as molybdenum and oil kiln carbon black (average size of particles: 15mp 2 (EM method), specific surface area: 200 m / g (BETg method in an amount of 2% by weight, respectively, in the case of example 31; and an aqueous solution of ammonium molybdenate dissolved in water in an amount of 500 ppm in the form of molybdenum to form an emulsion, or an alumina produced by vapor phase processes has been added mean particle size: 20 m (EM method), specific surface area: 100 m2 / g (BET method)] in an amount of 3% by weight in the case of Example 32.

The thermal cracking conditions were in each case a temperature of 4900C, a pressure of 150 bar, a residence time (based on the cold liquid) of 18 minutes and a hydrogen / feed ratio of 1500 Nl / l. , the number of revolutions of the stirrer being 1000 rpm.

The thermally cracked products liberated from the gaseous components were subjected to atmospheric and vacuum distillations in the respective separation step, as in Example 20 for the removal of the high boiling point components at a boiling point. above 5200C and the fraction boiling below 5200C has been steam pyrolyzed to obtain olefins and monocyclic aromatics
The results of the steam pyrolysis of Examples 31 and 32 are given in Table 4, as well as the yields of the main chemical raw materials (gaseous olefins and main monocyclic aromatics).

EXAMPLES 33 and 34.

Using an atmospheric residue of light Arabian crude (100% by weight of fraction having a boiling point above 3430C, 46% by weight of fraction having a boiling point above 5200C), as feedstock , thermal cracking was undertaken by the same equipment of the continuous type operating at high pressures as in Example 1.

For both kinds of components to be added to the feed oil in thermal cracking, pentacarbonyl-iron in an amount of 800 ppm was added as iron and carbon black to the tunnel average particle size: 15 method
EM), specific surface area: 300 m2 / g (BET method)] zip in an amount of 2% by weight, respectively, in the case of Example 33; and cobalt resinate in an amount of 300 ppm in the form of cobalt and thermal carbon black C Average particle size: 80 m (EM method), specific surface area 15 m2 / g (BET method) J in an amount of 6% by weight in the case of Example 34.

The thermal cracking conditions were, in each case, a temperature of 4700C, a pressure of 200 bar, a residence time (based on cold liquid) of 30 minutes and a hydrogen / feed oil ratio of 2000 Nl / l. , the number of agitator revolutions being 1000 rpm.

The thermally cracked products liberated from the gaseous components were subjected to atmospheric and vacuum distillations in the respective separation step for the removal of the high boiling point components having a boiling point above 5200C.

Using the fraction boiling below 520 ° C obtained as the feed oil, a hydrotreatment was carried out with the same continuous type hydrotreatment reaction device and the same fixed bed catalyst as in Example 19 in. the conditions of a hydrogen / feed oil ratio of 1000 Nl / l, a temperature of 395 "C, a pressure of 180 bars and an LHSV of 0.8 h
The recovered hydrotreated oil was steam pyrolyzed by a tubular heater type pyrolyzer under the conditions of an inlet temperature of 5500C, an outlet temperature of 8300C, an outlet pressure of 0.8 bar, a vapor / hydrogenated oil weight ratio of 1.0 and a residence time of 0.2 seconds to obtain olefins and monocyclic aromatics.

The results of the steam pyrolysis of Examples 33 and 34 are shown in Table 4, together with the yields of the main chemical raw materials (gaseous olefins and main monocyclic aromatics).

Table 4 Steam Pyrolysis Results and Yields of Major Chemical Raw Materials by Feedstock

Example <SEP> 31 <SEP> Example <SEP> 32 <SEP> Example <SEP> 33 <SEP> Example <SEP> 34
<tb> Hydrogen <SEP> 0.7 <SEP> 0.7 <SEP> 0.7 <SEP> 0.8
<tb> Methane <SEP> 10.3 <SEP> 10.1 <SEP> 11.3 <SEP> 11.6
<tb> Yield
<tb> Ethylene <SEP> 29.4 <SEP> 28.5 <SEP> 30.5 <SEP> 31.0
<tb> of <SEP> products <SEP> Propylene <SEP> 14.9 <SEP> 15.0 <SEP> 16.7 <SEP> 14.7
<tb> princi
Butadiene <SEP> 5.2 <SEP> 5.5 <SEP> 6.8 <SEP> 7.0
<tb> paux <SEP> (%
<tb> in <SEP> weight) <SEP> Aromatics <SEP> monocyclic <SEP> (C6 <SEP> to <SEP> C8) <SEP> 9.8 <SEP> 10.0 <SEP> 13.0 <MS> 12.1
<tb> Cracked <SEP> gasoline <SEP> (C5 <SEP> - <SEP> 200 C) <SEP> 16.4 <SEP> 16.8 <SEP> 21.8 <SEP> 19.5
<tb> Heavy <SEP> oil, <SEP> (plus <SEP> of <SEP> 200 C) <SEP> 19.2 <SEP> 18.8 <SEP> 8.8 <SEP> 9.2
<tb> Yield <SEP> of <SEP> raw materials <SEP> chemical <SEP> main
<tb> (% <SEP> in <SEP> weight) <SEP> (1) <SEP> 59.3 <SEP> 59.0 <SEP> 67.0 <SEP> 64.8
<tb> CONTINUED FROM TABLE 4

example <SEP> example <SEP> example <SEP> example
<tb> 31 <SEP> 32 <SEP> 33 <SEP> 34
<tb> Yield <SEP> of <SEP> thermally <SEP> oil <SEP> cracked
<tb> boiling <SEP> at <SEP> minus <SEP> of <SEP> 520 C <SEP> in <SEP> step <SEP> of
<tb> thermal <SEP> cracking <SEP> (% <SEP> in <SEP> weight) <SEP> (2) <SEP> 85.3 <SEP> 84.5 <SEP> 84.5 <SEP> 84 , 7
<tb> Yield <SEP> of <SEP> hydrotreated oil <SEP><SEP> in
<tb> hydrotreatment step <SEP><SEP> (% <SEP> in <SEP> weight) <SEP> - <SEP> - <SEP> 99.1 <SEP> 99.1
<tb> (3)
<tb> Yield <SEP> of <SEP> raw materials <SEP> chemical <SEP>
<tb> main <SEP> by <SEP> load <SEP> power supply
<tb> (% <SEP> in <SEP> weight) <SEP> (4) <SEP> 50.6 <SEP> 49.9 <SEP> 56.1 <SEP> 54.4
<tb> Note 1) Yield of main chemical raw materials = Yield of ethylene +
Yield of propylene + yield of butadiene + monocyclic aromatics (C6 to C8) 4) Yield of main chemical raw materials per feedstock = (1) X (2) X (3).

Claims (11)

recovering the resulting lighter hydrocarbon oil. thermally cracking the heavy hydrocarbon in the presence of hydrogen gas or hydrogen gas containing hydrogen sulfide; and adding to the heavy hydrocarbon at least two kinds of substances comprising an oil-soluble or water-soluble transition metal compound and an ultra-fine powder which can be suspended in a hydrocarbon and which has an average particle size between 5 and 1000 1.- Process for converting a heavy hydrocarbon into a product of greater value, characterized in that it consists in 2.- Process for converting a heavy hydrocarbon into a product of greater value, characterized in that it consists in: 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 disperse an ultra fine powder - having an average particle size between 5 and 1000 mF in the oil solution or in the oil / water emulsion heating the dispersion to the decomposition temperature of the compound of a transition metal in the presence of hydrogen gas or hydrogen gas containing hydrogen sulfide; separate a solid from the dispersion. ;; add the solid to a heavy hydrocarbon thermally cracking the heavy hydrocarbon in the presence of hydrogen gas or hydrogen gas containing hydrogen sulfide; and recovering the resulting lighter hydrocarbon oil. 3.- Process for converting a heavy hydrocarbon into a product of greater value, characterized in that it consists in dissolving an oil soluble transition metal compound in an oil or dissolving a water soluble transition metal compound in water converting the solution to a solid by spraying the solution into hydrogen gas or hydrogen gas containing hydrogen sulfide where an ultra-fine powder having an average particle size between 5 and 1000 mf is dispersed and simultaneously heating the gas to decompose the compound of the transition metal and to heat the solid; adding the resulting solid to a heavy hydrocarbon ;; thermally cracking the heavy hydrocarbon in the presence of hydrogen gas or hydrogen gas containing hydrogen sulfide; and recovering the resulting lighter hydrocarbon oil. 4.- Method according to any one of claims 1 to 3, characterized in that all or part of a solid which is separated and recovered from the lighter hydrocarbon oil or a residue obtained by distilling the hydrocarbon more lightweight is recycled. 5. A method according to any one of claims 1 to 3, characterized in that all or part of a residue obtained by distilling the lighter hydrocarbon is recycled. 6.- Process for the conversion of a heavy hydrocarbon into a lighter and higher value product, characterized in that it consists in hydrotreating the lighter hydrocarbon oil obtained in claims 1, 2, 3, 4 or under hydrotreating conditions and recovering the resulting hydrotreated oil. 7.- Process for the conversion of a heavy hydrocarbon into a lighter and higher value product, characterized in that it consists in removing a fraction having a high boiling point, from the higher hydrocarbon oil. light obtained in claims 1, 2, 3, 4 or 5, hydrotreating a fraction having a low boiling point under hydrotreating conditions, and recovering the resulting hydrotreated oil. 8.- Process for converting a heavy hydrocarbon into a product of greater value, characterized in that it consists in (A) add to a heavy hydrocarbon (i) at least two kinds of substances comprising an oil-soluble or water-soluble transition metal compound and an ultra-fine powder which can be suspended in a hydrocarbon and which has an average size particles between 5 and 1000 mf; or (ii) a solid prepared by dissolving an oil-soluble transition metal compound in an oil or by emulsifying an aqueous solution of a water-soluble transition metal compound in an oil by dispersing an ultra-fine powder having an average particle size of between 5 and 1000 mw in the solution in oil or in the oil / water emulsion and by heating the dispersion to the decomposition temperature of the compound of the transition metal present hydrogen gas or hydrogen gas containing hydrogen sulfide; or (iii) a solid prepared by dissolving an oil soluble transition metal compound in an oil or by dissolving a water soluble transition metal compound in water; and converting the solution to a dry solid by spraying the solution into hydrogen gas or hydrogen gas containing hydrogen sulfide where an ultrafine powder having an average particle size between 5 and 1000 is dispersed and simultaneously heating the gas to decompose the compound of the transition metal and to dry the solid. (D) pyrolyzing a fraction having a low boiling point or a mixture of the fraction and a petroleum fraction with steam, and recovering a gaseous olefin and a monocyclic aromatic product. (C) removing a high boiling fraction from the lighter hydrocarbon oil; and (B) thermally crack the heavy hydrocarbon in the presence of hydrogen gas or hydrogen gas containing hydrogen sulfide and recover the resulting lighter hydrocarbon oil a monocyclic aromatic product. with steam, and recover a gaseous olefin and hydrotreated oil and a petroleum fraction (E) pyrolyze hydrotreated oil or a mixture the resulting hydrotreated oil; and boiling under hydrotreatment conditions and recover (D) hydrotreat a fraction having a low point Lighter hydrocarbon oil boil (C) remove a fraction with a strong point resulting lighter carbide (B) thermally crack the heavy hydrocarbon in the presence of hydrogen gas or hydrogen gas containing hydrogen sulfide and recover the hycro oil solution to a dry solid by spraying the solution into hydrogen gas or hydrogen gas containing hydrogen sulfide where an ultra-fine powder having an average particle size between 5 and 1000 is dispersed and simultaneously heating the gas to decompose the compound of the transition metal and to dry the solid water soluble in water; and converting the (iii) a solid prepared by d. dissolving an oil soluble transition metal compound in an oil or by dissolving a transition metal compound or hydrogen gas containing hydrogen sulphide; or transition metal in the presence of hydrogen gas (ii) a solid prepared by dissolving an oil-soluble transition metal compound in an oil or by emulsifying an aqueous solution of a water-soluble transition metal compound in an oil by dispersing an ultrafine powder having an average particle size between 5 and 1000 mf in the solution in oil or in the oil / water emulsion and converting the dispersion to a solid by heating the dispersion to the decomposition temperature of the compound (i) at least two kinds of substances comprising an oil-soluble or water-soluble transition metal compound and an ultra-fine powder which can be suspended in a hydrocarbon and which has an average size particles between 5 and 1000 mfti; ; or (A) add to a heavy hydrocarbon 9.- Process for converting a heavy hydrocarbon into a product of greater value, characterized in that it consists in 10.- A method according to any one of claims 8 or 9, characterized in that all or part of a solid which is separated and recovered from the hydrocarbon oil more light obtained in step (B) or the fraction having a high boiling point removed in step (C) is recycled to Step (D). 11.- A method according to any one of claims 8 or 9, characterized in that all or part of the fraction having a high boiling point removed in step (C) is recycled to step (B).