DE2522313A1 - PROCESS FOR THE PRODUCTION OF HYDROCARBON PRODUCTS WITH IMPROVED QUALITY - Google Patents

Description

with improved quality

The invention relates to a method for extracting hydrocarbons Material products of improved quality made from a carbonaceous or carbonaceous material, such as shale oil solids, Tar sand solids, coal solids and / or a hydrocarbon fraction, by treating the carbonaceous or carbonaceous material with a dense, fluid material containing water at a temperature in the range of about 316 ° C (600 ° F) to about 482 ° C (900 ° F) in the absence of supplied hydrogen and in the absence or presence of an externally added catalyst system,

In the present application, the term "carbonaceous" also include the term "carbonaceous".

A promising process for the production of hydrocarbons of carbonaceous material is a process known as "extraction with a dense, fluid material or dense Fluid extraction ". In general, it is customary to refer to this process with the Anglo-Saxon expression, namely "dense fluid extraction". The separation through the

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Extraction with a dense, fluid material at elevated levels Temperatures is an area that has not been well explored. The basic principles of dense extraction with a fluid material at elevated temperatures are described in the monograph "The Principles of Gas Extraction" by P.F.M. Paul and W.S. Wise, published by Mills and Boon Limited in London, 1971. Chapters 1 to 4 are particularly important. fluid material can be either a liquid or a dense gas with a density similar to a liquid, be.

The extraction with a dense, fluid material depends on the changes in the properties of the fluid material, from, in particular the density of the fluid material, due to changes in pressure. At temperatures below its critical Temperature, the density of the fluid material varies in steps with changes in pressure. Such sharp transitions in of density are associated with vapor-liquid transitions. At temperatures above the critical temperature of a fluid Material, the density of the fluid material increases almost linearly with the pressure, as indicated by the gas equation for ideal gases is required, although deviations from linearity are observed at higher pressures. Such deviations are more pronounced when the temperature of the fluid material is closer to, but still above, its critical temperature.

Becomes a fluid material at a temperature below its critical temperature and at its saturated vapor pressure held, two phases will appear in equilibrium with each other, the liquid X with the density C and the vapor Y. with the density D. The liquid with the density C will have a certain solvent power. If the same fluid material then held at a particular temperature above its critical temperature and when it compresses to density C. If so, the compressed fluid material is expected to have a solvent power that is similar like that of the liquid X with the density C. A similar solvent force can be carried out at an even higher temperature

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an even greater compression of the fluid material up to density C can be achieved. Because of the non-ideal behavior however, of the fluid material close to its critical temperature, a particular increase in pressure will be more effective in order to to increase the density of the fluid material when the temperature is slightly above the critical temperature than when the temperature is much higher than the critical temperature of the fluid material.

These simple considerations have led to the suggestion that at a given pressure and temperature above the critical temperature of the compressed fluid material, the dissolving power of the compressed fluid material is greater should be the lower the temperature, and that at a given temperature above the critical temperature of the compressed fluid material, the solvent power of the compressed fluid material should be greater to the higher the pressure.

Although such beneficial solvent effects have been found above the critical temperature of the fluid solvent, it is not essential that the solvent phase be over their critical temperature is maintained. It is only essential that the fluid solvent be at sufficiently high pressures is held so that its density is high. Thus, liquid fluid materials and gaseous fluid materials are the maintained at high pressures and which have liquid-like densities, are useful solvents in extraction with a dense, fluid material at elevated temperatures.

The basis for separations with a dense, fluid material at elevated temperatures is that a substrate is in Contact with a dense, compressed fluid material at an elevated temperature is brought, with material from. If the substrate dissolves in the phase of fluid material, then the phase of fluid material that contains the dissolved material contains, isolated, and then the isolated phase of the fluid material is decompressed to a point where the

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Solvent power of the fluid material is eliminated, and then the dissolved material separates as a solid or as a liquid.

Such general considerations based on empirical relationships based, were carried out with a view to the conditions to ensure a high solubility of the substrates in dense, to achieve compressed fluid materials. For example, the solvent action depends on a dense, compressed fluid material on the physical properties of the fluid solvent and the substrate. This concludes suggest that fluid materials with different chemical natures but similar physical properties turn out to be Behave similarly to solvents. An example is the finding that the solvent power of compressed ethylene and Is similar to carbon dioxide.

Furthermore, it was concluded from these considerations that a more efficient extraction can be obtained with fluid material could be with a solvent whose critical temperature closer to the extraction temperature than with a solvent whose critical temperature is further from the Ex- traction temperature is away. Because the solvent power of the dense, compressed fluid material should be larger the lower the temperature, but as the vapor pressure of the material to be extracted should be larger, the higher the temperature, the choice of extraction temperature must be a compromise between these opposing effects be.

Various ways of practically using extraction with a dense, fluid material are possible analogous to known separation processes. For example, the extraction stage and the decompression stage enable considerable latitude for performing separations of mixtures of materials. Mild conditions can be chosen to extract the more volatile materials first, and then tougher conditions can be

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to extract the less volatile materials. The relaxation or decompression stage can also be carried out in a single stage or in several stages so that the less volatile First separate the loosened species. The extent of extraction and the recovery of the product during decompression can be regulated by choosing a suitable fluid solvent, the temperature and pressure during the extraction or adjusted during decompression and by changing the ratio of substrate to fluid solvent with which the extraction vessel is charged.

In general, extraction with a dense, fluid material at elevated temperatures can be used as an alternative to the one hand distillation and, on the other hand, extraction with liquid solvents at low temperatures will. A notable advantage of extraction with a dense, fluid material over distillation is that it is possible to treat substrates with low volatility. The extraction with a dense, fluid material is often an alternative to molecular distillation because of the very high concentrations in the phase of the dense, fluid material occur, so that one obtains great advantages in the passage. Extraction with a dense, fluid material is special Useful when heat-sensitive substrates have to be treated, as the extraction takes place in the dense, fluid phase Material is possible at temperatures that are significantly below those required for distillation.

A major advantage of extraction with a dense, fluid Material at elevated temperatures, compared to liquid extraction at low temperatures, is that that the solvent power of the compressed fluid solvent can be continuously regulated by the Pressure instead of temperature. The possibility that Regulating solvent force through changes in pressure opens up new possibilities and applications for solvent extraction process.

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Zhuze was obviously the first to use the extraction a dense, fluid material used in chemical-technical processes to free petroleum fractions from the asphalt, using a propane-propylene mixture as gas, as stated in Vestnik Akad. Nauk S.S.S.R. 29_ (11), 47-52 (1959) and in Petroleum (London) 23, 298-300 (1960).

Apart from the work of Zhuze, there have been hardly any reports in the literature of attempts to use extraction processes with a dense, perform fluid material with substrates of technical interest. In GB-PS 1 05 7 911 (1964) the principles of gas extraction is described in general terms and its use as a separation process complementary to Solvent extraction and distillation are illustrated, and a multi-step process is described. In GB-PS 1 111 (1965) describes the use of a gas extraction process for processing heavy petroleum fractions. One Of particular interest is the separation of materials into a residue and extraction products, whereby the the latter are free from harmful inorganic impurities such as vanadium. The advantage of the gas solvent cooling to subcritical temperatures before recycling is also indicated in this patent. As a result, it is converted into the liquid form, which has less energy for pumping compared to the hydrostatic head in the Reactor requires as gas. In FR-PSs 1 512 060 (196 7) and 1 512 061 (196 7) the use of gas extraction described for petroleum fractions. In principle, these references follow the direction of earlier Russian work.

In addition, there are other references in which the extraction of liquid hydrocarbon fractions from carbonaceous Materials using water in these methods. For example, will in US Pat. No. 3,051,644 (1962) describes a process for extracting oil from oil shale, in which the oil shale particles dispersed in steam and with steam at a temperature in the range of 371 ° C (700 ° F) to 482 ° C (900 ° F) and a pressure

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in the range of 70.3 to 210.9 atmospheres (1000 to 3000 psig). The oil from the oil shale is in vapor form taken mixed with water vapor.

US Pat. No. 2,665,238 (1954) describes a process for extracting oil from oil shale in which the shale is mixed with water in large quantities, based on the weight of the shale, at a temperature above 260 ° C (500 ° F ) and treated at a pressure in excess of 70.3 kg / cm (1000 psi). The amount of oil recovered generally increases as the temperature or pressure is increased further, but pressures as high as 210.9 atmospheres (3000 psig) and temperatures as high as 371 ° C (700 ^° F) are required to recover substantially all of the oil.

In US Pat. No. 2,665,390 (1948), a process is described in general explanations in which coal is dissolved in liquid solvents dissolved at high temperatures and then the solution in a charring device or coking device is atomized, but the supercritical conditions are not mentioned. In the US Defensive Publication 700 (filed January 25, 1968) describes the use of a gas extractant to extract from a solution of Coal in a liquid solvent to recover a fraction that is used as feed for hydrocracking is suitable for motor gasoline.

In U.S. Patent 3,642,607 (1972) a method of solving the problem is disclosed of bituminous coal by heating a mixture of bituminous coal and a hydrogen donor oil, carbon monoxide, Water and an alkali metal hydroxide or a precursor at a temperature of about 400 to 450 ° C and one Total pressures of at least about 281 atmospheres (4000 psig) are reported.

U.S. Patent No. 3,687,838 (1972) describes the same procedure as that described in U.S. Patent No. 3,642,607 (1972), but with this one Process, an alkali metal or ammonium molybdate

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place of the alkali metal hydroxide or its precursor.

US Pat. No. 3,796,650 (1974) describes a process for deashing and liquefying coal, in which crushed coal is mixed with water, at least part of which is in the liquid phase, with a reducing gas supplied from the outside and a compound, such as ammonia or alkali metal carbonates or hydroxides, is treated under liquefaction conditions including a temperature of 200 to 3 70 ° C to a
to manufacture hydrocarbon containing product.

There are numerous references for processes for cracking (cracking), for desulfurization, for denitrification,
for demetallization and generally for improving the quality of hydrocarbon fractions in which water
is also used. For example, U.S. Patent 3,453,206 (1969) discloses a multistep process for hydrofining
heavy hydrocarbon fractions described in which
the concentration of sulfur-containing, nitrogen-containing,
organometallic and asphaltenic impurities are to be removed or reduced therefrom. The nitrogenous and sulfurous impurities are converted into ammonia
and hydrogen sulfide transferred. In these procedures
the hydrocarbon fraction in the absence of a catalyst with a mixture of water and "externally fed."
Hydrogen at a temperature above the critical temperature of water and at a pressure of at least 70.3 atü
(1000 psig) and then the liquid product
reacted from the pretreatment stage with externally supplied hydrogen under hydro refining conditions and in the presence of a catalytic mass. The catalytic mass contains a metal component together with a refractory inorganic oxide carrier material of either synthetic or natural origin, the carrier material having a medium to high surface area and a well-developed pore structure. The metal components that can be used are vanadium, niobium, tantalum, molybdenum, tungsten, chromium, iron,

Cobalt, nickel, platinum, palladium, iridium, osmium, rhodium, ruthenium and mixtures thereof.

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In US Pat. No. 3,501,396 (1970) a method for desulfurization is disclosed and denitrification of oil described in which the oil with water at a temperature above the critical Water temperature up to about 427 ° C (800 ° F) and mixing at a pressure in the range of about 70.3 atmospheres (70.3 psig) to about 175.8 atmospheres (2500 psig) and wherein, then the resulting mixture is reacted with externally supplied hydrogen in contact with a catalytic mass will. The catalytic mass can be described as a catalyst with a dual function and contains a metal component, such as iridium, osmium, rhodium, ruthenium or mixtures thereof and an acidic carrier component with cleavage activity. An essential one The feature of this process is that the catalyst is acidic in nature. Ammonia and hydrogen sulfide are formed during the conversion of nitrogen-containing and sulfur-containing compounds.

In U.S. Patent No. 3,586,621 (19 71) a method of conversion is disclosed heavy hydrocarbon oils, residual hydrocarbon fractions and from solid carbonaceous material described in more useful gaseous and liquid products, in which the material that is to be converted with a nickel spinel catalyst, which is treated with a barium salt organic acid is activated, is treated in the presence of water vapor. A temperature in the range of 316 ° C to about 538 ° C (600 to 1000 ° F) and a pressure in the range of 14.1 to 211 atmospheres (200 to 3000 psig) is used.

US Pat. No. 3,676,331 (1972) describes a method for improving quality of hydrocarbons, including materials with low molecular weight and reduced, Sulfur content and carbon residue formed by adding water and a catalyst system that has at least two Contains components to which the hydrocarbon fraction is added. The water can be the natural water content of the hydrocarbon fraction or it can be added to the hydrocarbon fraction from an external source. The water to hydrocarbon fraction volume ratio is imminent-

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added in the range of about 0.1 to about 5. At least the first of the components of the catalyst system will benefit the formation of hydrogen by the conversion of water in the water-gas rearrangement reaction, and at least the second Part of the catalyst system favors the conversion between the hydrogen formed and the constituents the hydrocarbon fraction. Suitable materials to be used as the first component of the catalyst system are the carboxylic acid salts of barium, calcium, strontium and magnesium. Suitable materials as the second component The carboxylic acid salts of nickel, cobalt and iron can be used in the catalyst system. The procedure is at a reaction temperature in the range of about 399 ° C to about 454 ° C (750 to 850 ° F) and a pressure of about 21.09 to about 281 atmospheres (300 to 4000 psig), so that most of the crude oil remains in a liquid state.

U.S. Patent No. 3,733,259 (1973) discloses a process for removing metals, asphaltenes, and sulfur from heavy hydrocarbon oil described. In this process, the oil is dispersed with water, this dispersion is used in a Temperature maintained between 399 and 454 ° C (750 and 850 ° F) and a pressure between atmospheric and 7.03 atg (100 psig), the dispersion is cooled after at least 1/2 hour in order to form a stable water-asphaltene emulsion, then the emulsion is separated from the treated oil, hydrogen is added and the resulting treated oil is operated with a hydrogenation catalyst at a temperature between 260 and 482 ° C (500 and 900 ° F) and a pressure between treated approximately 21.09 and 122 atmospheres (300 and 3000 psig).

It was also stated that the partially state Japanese Atomic Energy Research Institute working with Chisso Engineering Corporation, a process developed, which is called "simple, low-cost, hot-water, oil desulfurization process" and which one

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should have sufficient technical applicability to deal with to compete with the hydrogenation process. The process itself consists of putting oil through one under pressure standing boiler water tank in the water at about 250 ° C under a pressure of about 100 atmospheres is heated. The sulphides in the oil are separated when the water temperature is lowered below 100 ° C.

As far as the applicant is aware, the process according to the invention for the production of hydrocarbon fractions with improved quality from carbonaceous materials not yet described. The method according to the invention enables working in a single stage at temperatures that are lower than those normally used, without an external source of hydrogen and without a production or pretreatment, such as desalination or demetallization, before the quality of the recovered hydrocarbon fraction is improved.

Embodiments according to the invention are explained with reference to the accompanying drawings.

Fig. 1 is a graph showing the relationship of the weight loss in calcining oil shale with the results of Fischer analysis of these solids.

^{A series of graphs are shown in} FIG. 2 which show the temperature dependence of the yields of hydrocarbon product from oil shale in the process according to the invention.

3 is a series of graphs showing the dependence of the yields of oil and bitumen from oil shale on the particle size of the oil shale and on the contact time using the method of the invention.

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4 is a series of graphs showing the dependence of the oil selectivity on the particle size of the oil shale and on the contact time in the process of the invention.

Figure 5 is a series of graphs showing the hexane yield using 1-hexene as the starting material for different amounts of catalyst in the presence of an equal amount of activator.

Fig. 6 is a graph showing the hexane yield using 1-hexene as the starting material as a function of different amounts of activator in the presence of a given amount of catalyst.

Figure 7 is a schematic representation of the flow sheet that can be used for semi-continuous treatment of a hydrocarbon fraction.

It has been found that hydrocarbons from carbonaceous Materials can be recovered and that the quality of the recovered hydrocarbons can be improved that they can be cracked, desulfurized and, if the carbonaceous material is tar sand solids, oil shale solids or a hydrocarbon fraction, the paraffins, olefins, Contains olefin equivalents or acetylenes as such or as substituents on ring compounds, it is demetallized and can optionally be hydrogenated and freed from nitrogen by the carbonaceous material with a dense, Phase containing water, either a gas or a liquid, at a reaction temperature in the range of about 316 ° C to about 482 ° C (600 to 900 ° F), i.e. from about 315 to about 485 ° C, in the absence of additional feed Hydrogen and depending on the type and extent of the desired quality improvement, in the absence or presence an externally added catalyst system,

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acts. When the carbonaceous material is a solid carbon is, the solid coal remaining after the treatment by the method of the present invention can be desulfurized. This procedure is feasible with the whole range, i.e. with all hydrocarbon fractions, including both light materials and heavy materials such as gas oil, residual oils, tar sand oil, oil shale kerogen extracts and liquefied coal products.

It has been found that in order to effect the recovery of the hydrocarbons from the carbonaceous material and the to achieve chemical conversion of recovered hydrocarbons into lighter, more useful hydrocarbon fractions, in the process according to the invention - in which process steps are carried out, which are characteristically in solution and that does not occur in typical pyrolytic processes Water in the phase of dense fluid material, which contains water, has a high solubilizing power and is liquid-like Must have densities, for example at least 0.1 g per ml and not vapor-like densities. The presence of Water in the dense, water-containing phase with a relatively high density is essential in the process according to the invention, both at temperatures below and above the critical temperature of the water. The density of the water in the dense phase, which contains water, must be at least 0.1 g per ml.

The high solvent power of dense, fluid materials is described in the monograph "The Principles of Gas Extraction" by P.F.M. Paul and W.S. Wise, published by Mills and Boon Limited in London, 1971. For example, the difference in the solvent power of water vapor and dense gaseous water that is at a temperature in the range of the critical temperature of the water and at elevated Pressure is maintained essential. Even usually insoluble inorganic materials, such as silicon dioxide and aluminum oxide, begin to dissolve noticeably in "supercritical water", i.e. water which is at a temperature above

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the critical temperature of the water is maintained as long as a high water density is maintained.

Sufficient water must be used so that there is sufficient water in the water-containing, dense phase, making it an effective solvent for the recovered hydrocarbons can work. The water in the water-containing, dense phase can either be liquid or water be present as dense gaseous water. The vapor pressure of the water in the dense, water-containing phase must be a sufficiently high value so that the density of the water in the dense, water-containing phase at least 0.1 g per ml.

It has been found that due to the limitations imposed by the size of the reaction kettles that are used can, given, a weight ratio of hydrocarbon fraction to water in the water-containing, dense Phase in the range of about 1: 1 to about 1:10 is preferred and that a ratio in the range of about 1: 2 up to about 1: 3 is most preferred. Similar is a weight ratio of oil shale, tar sands, or coal solids to water in the water-containing, dense phase in the range of about 3: 2 to about 1:10 preferred, and a ratio in the range from about 1: 1 to about 1: 3 is most preferred.

A particularly useful water-containing fluid material contains water along with an organic compound such as Biphenyl, pyridine, a partially hydrogenated aromatic oil, or a mono- or polyvalent compound such as methyl alcohol, The use of such combinations increases the limits of solubility and dissolution rates, so that the Fissures, hydrogenation, desulfurization, demetallization and denitrification can take place even more easily. Furthermore, a component that is different from water, in the dense phase containing water as a source of hydrogen, for example by reacting with water.

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If in the method according to the invention a sulfur and Nitrogen-resistant catalyst, such as at least one soluble or insoluble transition metal compound or transition metal, deposited on a support, or mixtures thereof, is used, such a catalyst is effective, when added in an amount equivalent to the concentration in the water of the water-containing fluid Material in the range of about 0.02 to about 1.0 weight percent, and preferably in the range of about 0.05 to about 0.15% by weight.

If such a catalyst is in the water containing fluid Material is not soluble, then it can be added as a solid and slurried in the reaction mixture. Alternatively, the catalyst can be deposited on a carrier and slurried in the water-containing fluid material will. Charcoal, activated carbon, refractory alumina and oxides, such as silicon dioxide, aluminum oxide, manganese dioxide and Titanium dioxide, has been used with success as a carrier for insoluble catalysts. However, silica and alumina are with a high surface area is only satisfactory as carriers when used at reaction temperatures below the critical temperature of water.

Any suitable method of depositing a catalyst on a support can be used. A suitable method consists in immersing the support in a solution containing the desired weight of catalyst dissolved in a suitable solvent. The solvent is then removed and the support with the catalyst deposited thereon is dried. The support and catalyst are then placed in a stream of inert gas at about 500 ° C for about Calcined for 4 to 6 hours. The catalyst can then be reduced or oxidized as desired.

If in the method according to the invention a sulfur-resistant Catalyst, such as at least one basic metal carbonate, basic metal hydroxide, transition metal oxide, an oxide-forming

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of the transition metal salt or combinations thereof is, such a catalyst is effective when it is in an amount equivalent to a concentration in the water of the Fluid material containing water in the range from about 0.01 to about 3.0% by weight and preferably in the range from about 0.10 to about 0.50 weight percent is added.

Such catalysts can be added as a solid and slurried in the reaction mixture, or they can be added as a water-soluble salt, for example as manganese chloride or potassium permanganate, the forms corresponding oxide under the conditions which are used in the process according to the invention. Alternatively can the catalyst can be deposited on a support and used as such in a fluidized bed, or it can be slurried in the water-containing fluid material.

The process can be carried out either batchwise or continuously or semi-continuously. Contact or Residence times between the carbonaceous material and the dense, water-containing phase, i.e. the residence time in a batch process, or conversely, the solvent space velocity in a flow process can be on the order of minutes up to about 6 hours and are satisfactory to a effective cleavage, hydrogenation, desulfurization, demetallization and denitrification of the hydrocarbons obtained reach.

In the process according to the invention, the water-containing, fluid material and the oil shale, tar sands or coal solids are contacted by one Slurry of oil shale, tar sand, or coal solids carried out in the water-containing, fluid material.

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If the method according to the invention is above ground with mined Oil shale, tar sand or coal is carried out, the hydrocarbons can be extracted more quickly if the mined Solids are milled, preferably to a particle size of 1.27 cm (1/2 inch) or less smaller. Alternatively, the method according to the invention can also be carried out in situ in the case of underground deposits by pumping the water-containing fluid material into the deposits and removing the hydrocarbon products, to separate or process them.

The following examples illustrate the invention.

Examples 1 to 38

Examples 1 to 38 relate to the batch processing of oil shale and tar sands as feed materials a variety of conditions and explain that hydrocarbons obtained by the process according to the invention, split, desulphurized and, if the carbonaceous material is an oil shale ο the a tar sand solid or a Hydrocarbon fraction is the paraffins, olefins, olefin equivalents or contains acetylenes or those as substituents on ring compounds, demetallized and optionally can be hydrogenated and freed from nitrogen. Unless otherwise specified, the following procedure will be used in each case used. The oil shale or tar sands as feed material, water and, if used, the components of the catalyst system are in a 300 ml Hastelloy alloy at ambient temperature C Magne-Drive autoclave in which the reaction mixture is mixed. The components of the catalyst system are added as solutions in water or as solids in slurries in water. Unless otherwise indicated, sufficient water is added in each example so that at the reaction temperature used, that used Pressure and the reaction volume used, the density of the water is at least 0.1 g per ml.

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The autoclave is flushed with an inert argon gas stream and then closed. This inert gas was also added, to increase the pressure in the reaction system. The contribution of argon to the total pressure at ambient temperature is called argon pressure.

The temperature of the reaction system is then increased to the desired value, and the phase from the dense, fluid Material containing water is formed. Approximately 28 minutes are required to get the autoclave from ambient temperature heat up to 349 ° C (66O ° F). It takes approximately 6 minutes for the temperature to rise to 349 ° C (66O ° F) 371 ° C (70 ° F) to increase. Approximately another 6 minutes are required to raise the temperature from 371 ° C (700 ° F) to 393 ° C (750 F). When the desired final temperature is reached the temperature is kept constant for the desired period of time. This constant final temperature and the reaction time at this temperature the reaction temperature and reaction time are defined. During the response time will the pressure of the reaction system increases as the reaction proceeds. The pressure at the beginning of the reaction time is called the reaction pressure Are defined.

After the desired reaction time at the desired reaction temperature and pressure has expired, the dense phase of fluid material, which contains water, is relaxed and "flash-distilled" from the reaction vessel (with relaxation distilled) to remove the gas, water and "oil" and being in the reaction vessel "bitumen", more inorganic Residue and components of the catalyst system, if one Catalyst system was used, remain. The "oil" is the liquid hydrocarbon fraction which boils at or below the reaction temperature, and the "bitumen" is the hydrocarbon fraction, which boils above the reaction temperature. The inorganic residue is used slate or spent tar sand.

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The gas, the water and the oil are in a pressure vessel, which is cooled with liquid nitrogen, collected. The gas is removed by bringing the pressure vessel to room temperature heated and then examined with mass spectroscopy, gas chromatography and infrared spectroscopy. The water and the oil are then flushed out of the pressure vessel with compressed gas, occasionally also by heating the Boiler. Then the water and oil are separated by decanting. The oil is based on its sulfur and nitrogen content using X-ray fluorescence and the Kjeldahl method, and its density and API specific Weight are determined.

The bitumen, the inorganic residue and the components of the catalyst system, if any, are removed from the reaction vessel washed out with chloroform, and the bitumen is dissolved in this solvent. The solid residue will then separated from the solution containing the bitumen by filtration. The bitumen is based on its sulfur and nitrogen contents analyzed using the same procedures as for oil analysis. The solid residue will analyzed for its inorganic carbonate content.

To extract hydrocarbons from oil shale, various have been used Samples of oil shale obtained from the Colorado oil shale deposits examined. These samples were obtained in the form of lumps, which were then ground and sieved, giving fractions of different Particle size received. About the kerogen content of these fractions To determine, portions of each sample were calcined in air at 53 8 C (1000 F) for 30 minutes to contain water and kerogenic carbon Remove materials without decomposing the inorganic carbonate. The particle size of the samples from oil shale, used and the percent weight loss during calcination for each of these samples are given in Table I.

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In Examples 1 to 3 7 the hydrocarbons were off the oil shale samples given in Table I below Using the method described above, obtained in batches. These attempts were made in a 300 ml Hastelloy alloy C Magne-Drive autoclave. The experimental conditions and the results obtained for these examples are given in Tables II and III below.

In these examples the liquid hydrocarbon products classified as either oils or bitumens, depending whether or not there are no liquid products from the autoclave and when releasing the pressure at the test temperature used could be distilled off. Oils are such liquid products that distill off by relaxation at the test temperature, while bitumens are liquid products that remain in the autoclave. The oil fractions have densities im Range from about 0.92 to about 0.94 g per ml and API specific weights in the range from about 19 API to about 23 API. The bitumen fractions have densities of approximately 1.01 g per ml and API-specific weights of approximately Oil shale sample A contains 0.7% by weight sulfur and 1.7% by weight nitrogen.

Table I.

Oil shale
sample 1)
Particle size Percent weight
loss during
the calcination A. 0.25-0.177 (60 - 32.2 B. 1.4-0.59 (14 - 26.8 C. 2.38-1.4 (8 - 36.6 D. - 80) 22.3 - 28) - 14) 0.6 - 0.3 ²⁾ (1 / 4-1 / 8) ²⁾

1) mm (mesh), unless otherwise stated.

2) Diameter in cm (inch).

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slate
sample ι) Reaction temp .
o _{c (} o _F ) (752) Reak
ions
time 3) Table II (4200) Argon-,,
pressure ^d)
atü (psig) Amount of
added
water ■ at
game A. 400 (660) 2 Reaction
pressure 2)
atü (psiq) (2550) 28.1 (400) 60 i
to- slate-to-
. Water weight
^4J relationship 1 A. 349 (752) 2 295 (4550) 28.1 (400) 60 1.0 2 A. 400 5 (715) ■ 2 179 5 (3450) 21.1 (300) 90 1.0 3 A. 379 ,! (752) 2 320 (4300) 21.1 (300) 90 0.56 4th A. 400 (752) 2 242, (4600) 21.1 (300) '90 0 _t 56 5 A. 400 (752) 2 302 (4100) 21.1 (300) 90 0.56 65 A. 400 (752) 2 323 (4100) 28.1 '(400) 90 Iv
0.56 ^ 7th A. 400 (752) 2 288 (4100) 28.1 (400) 90 0.56 .00 A. 400 (752) 2 288 (4100) 2 8.1 (400) 90 0.56. 9 A. 400 (752) 2 288 (4100) 28.1 (400) 90 '0.56 10 A. 400 • (752) 2 288 (4100) 28.1 (400) 90 . 0.56 11 C. 400 2 288 28.1 (400) 60
• 0.56
• NJ 12th 288 NJ
CO

Table II (porting)

• ■ at
game slate
sample 1 / Reaction
temperature
⁰ C ( ⁰ F) (752) Reak
ions
time 3) Reaction
pressure ² >
atü (psiq) (4200) Argon-
pressure ² >
atü (psiq) (400) 13th B. 400 (752) 2 , 295 (4200) 28.1 (400) en 14th C. 400 (752) 2 295 (4200) 28.1 (400) O 15th B. 400 (752)
(752) 2 295 (4100)
(4200) 28.1 (250)
(250) co
ο 16
17th C *
C. 400
400 (752) 1
1 288
295 . (4200) 17.6
17.6 (250) «Ο - ^:
O . 18th B. 400 (752) 1 295 (4200) 17.6 (250) he" 19th C. 400 (752) 0.5 295 (4200) 17.6 (250) 20th B. 400 (752) 0.5 • .295 (4100) 17.6 (250) 21 A. 400 (752) 1 . 288 (4100) 17.6 (250) 22nd A. 400 (716) 0.5 ■ 288 (3500) 17.6 (250) 23 C. 380 (716) 2 246 (3500) 17.6 (250) 24 B. ; 380 2 246 17.6

Amount of too
added
Water ⁴ ^ Crooked he-to-
Water weight * -
relationship 60 1.0 90 0.56 90 0.56 90 0.56 90 0.56 90
90 0.56.
£ 0.56 90 0.56 90 . 0.56 90 - 0.56 .90 0.56 90 ro
0.56 αϊ
ro
I NJ

Table II (continued)

' At
game slate
sample 1) Reaction
temperature
⁰ C (Op) (752) React
tion.
time ^i} Reactive
onsdruck "
atü (psig) (4250) argon
pressure 2)
atü (psig) (25.0) Amount of too
added
Water ⁴ ' Slate-to-
Water gevu-
relationship • 25223 25th D. 400 (752) 2 ' 299 (4150) 17.6 (250) • 90 0.56 26th D. 400 (698) 0.5 -.292 (3150) 17.6 (250) ■ 90 0.56 27 D. 371 (716)
(752) 0.5 221 (3500)
(3900) 17.6 (250)
(250) 90 _m 0.56 50985 28
29 'B
C. 380
400 (752) 2
13 6) 246
274 (3700) 17.6
17.6 (250) 90
60 0.56
1 O
■ * · «» 30th C. 400 (752)
(752) 8 ⁶⁾ 260 (3700)
(3950) 17.6 (250)
(250) " 60 i O
O
cn .31
32 C.
B. 400
400 (752) 3 6)
13 6) 260
278 (3950) 17.6
17.6- (250) 60
60 1
1 t
r 33 B. 400 (752) 3 6) 278 (4200) 17.6 (250) 60 1 34 D. 400 (752) 13.6) 295 (3900) 17.6 (250) 90 . 0.56 35 D. 400 (752) 3 6) 274 (4300) 17.6 (400) 60 1 . · 367 A. 400 (752) 2 • 302 (4300) 28.1 (400) 60 1 ' 37 ⁸ A. ■ 400 2 302 28.1 60 1
I.

Table II (continued)

Remarks

D The samples correspond to the letters given in Table I.

2) atü (psig)

3) hours, unless otherwise stated.
cn

α 4) g

_cn 5) This experiment was carried out using the back

° was in the autoclave used, which after releasing the gas, water ₍

it and oil product from the experiment in Example 5 remained. r \ j

° '6) minutes ι

cn.

7) The water also contained 0.1% by weight of soluble RuCl ₃ * 1-3HpO and 0.6% by weight of soluble sodium carbonate catalyst.

8) The water also contained 0.6% by weight of soluble sodium carbonate ; catalyst.

en
ο at
game co ₂ *
Product composition a- Gases ^C 2 + total ) Tabel 8.3 slate Sulfur- bitumen Nitrogen- d Weight C) • CD
OO
at 1 6.8 CH ₄ 0.3 7.9 8.1 69.3 qehalt ^b) 0.31 qehalt ^] d rest b . ο 2 6.8 H ₂ 0.8 d 6.8 ! III 6.5 85.3 oil d b) d 101, 8th ώ 3 7.5 d 0.1 1.0 9.0 12.6 67.8 0.45 d Oil bitumen d 97 5 crt 4th 7.6 d 0.6 0.7 8.8 Liquids used 4.2 72.6 d d d d 99 7th • 5 &
6ft 11 d 0.4 0.2 11.7 Oil bitumen 8.7 70.2 d d d d 100, 4th 7th £ d 0 _; 6th f 9.7 13.2 10.3 69.4 d d d d 101, 6th ■ 8 f d f f 8.7 0.5 7.5 69.4 ' d d d d 100, 7th on
ro 9 f f £ f 8.8 13.5 7.3 69.6 d d d d 101, 6th 10 f f f f 9.2 8.4 10.2 68 _T 8 d d d d 101, 6th 11 f £ f f 9.8 15.8 9.2 66.5 d d d 2.0 101, 6th 12th 6.3 f f d 9.7 13.7 66.0 d 0.37 d 101, 8th
> f 0.8 13.0 d d 101,
I. 0.2 15.2 0.48 d 16.0 1.3 . 14.9 17.8

Table III (continued)

at
game co ₂ Product composition a) Gases ^C 2 ₊ total !Liquids 9.0 ■ ■ sulfur— 3i gymnastics Stick StO ^ rF- b) I * ⁵ Gew # - 13th 7 _V 8 CH ₄ d 6.0 Oil bitumen 7.4 Consumed qehalt b) 0.38 keep Oil bitumen d Re st 14th 7.5 H ₂ 0.7 d 10.8 11.8 5.0 slate Oil] d 1.3 d 100.3 15th V 0.2 0.8 d 11.0 14.4 11.0 77.8 0.45 d d d 100.2 .16 6.18 0.2 0.6 d - ■ 10 _; 5 11.8 68.0 d d d 2.5 101.9 cn 17th 7.6 0.2 0.68 d 11.0 11.2 6.4 76.8 d 0.43 • d 2.2 - ο
CO
OO 18th 5.6 0.18 0.6 d 10.6 11.0 12.4. 67.8 d 0.62 2.0 101.7 cn
O 19th 5.2 0.1 0.4 d 8.0 9.5 8.0 66.4 0.32 0.38 . 1.3 2.1 100.6 O 20th • 5.9 d 0.4 d 8.8 ll _t 3 9.7 75.0 0.49 0.55 If3 2.2 100.4 O
cn 21 .6.1 d 0.3 d 8.8 9.6 ■ 13.0 68.4 0.36 0.52 1.2 2.21 101.1 22nd 6.2 0.03 0.5 d 6.8 13.1 14.6 76.6 ' 0.60 0.69 1.3 2.04 99.7 23 7 _f 78 0.03 0.4 d 4.4 ^s 11.2 9 * 0 69.2 0.56 0 ₇ 28 1.27 1.94 99.6 24 d8 d 0.5 * d 11.8 69.3 0.67 0.46 1.16 - 0.07 ⁸ _d 8 7.2 69.2 0.75 I, " - d ⁸ 74.6 0.80

Table III (port setting)

at
game * Product additions a) Gases fs + total liquids 6.1 Consumed ■ sulfur bitumen nitrogen
Xm. \ • 2.10 : - Weight * - 25th ^CH 4 d 10.8 oil bitumen 6.5. • slate qehalt i>) 0.53 keep 2.04 Rest" 26th CO ₂ 0.6 d 7.8 8.8 5.0 76.0 oil 0.65 : ° i d 100.3 27 8.0 0.025 0.4 d 6.2 6.4 10.0 78.4 0.51 0.84 Oil bitumen 2.16 99.7 28 6.8 d 0.2 d - 8.6 4.4 17.5 87.3 0.81 0.37 1.72 2.41 100.0 . 29 6.0 d 0.4 d 7.9 7.0 13.4 76.0 1.06 0.52 . 1.37 100.2 cn 30th 6.3 0.025 0.23 d ■ 7.1 7.0 10.7 65.2 0.42 0.58 1.38 1.83 100 pounds ο
to
CX) 31 4.4 • d 0.18 d 7.2 5.6 7.6 71.3 0.86 0.69 1.28 1.68 99.5 crt
Q 32 3.9 d 0.07 d 8.3 4.0 · 8.3 • '80.0 0.68 0.37 1.16 2.17 101.5 i 4 33 3.0 d 0.19 d 6.3 5.5 5.7 78.7 0.93 0.46 2.09 100.3 \ S 34 6.9 d 0.07 d 8.3 5.8 9.8 79.2 0.57 0.42 1.03 2 _r 20 100.1 35 3.0 d 0.19 d 5.7 6.3 6.5 80 _t 9 0.77 0.53 1.38 100.5 36 6.5 d 0.07 0.4 9.0. 5.7 6.5 81.8 0.70 0.35 1.00 100.5 37 2.8 d. 1.0 0.3 6.0 16.0 " 70.5 0.80 0.37 1.14 101.5: 7.8 0.2 0.6 17.3 71.7 0.41 0.90 1O1 pounds 1. ■
^; 7.3 0.2 0.43 . ■ - -

Table III (continued)

Remarks

a)% by weight of the oil shale feedstock

b)% by weight of the particular fraction.

c) Total weight of feed materials shale and water and catalysis

d) not determined

cn and catalyst recovered as product and water

_o e) The experiment in Example 6 was carried out using the solid,

"" * · Substrate the residue in the autoclave after relaxing and ab- i \>

° .. co

-4 " ^{1. 1} distill the gas, water and oil product from the experiment in.

^ _n Example 5 used. The products of Examples 5 and 6 were

combined.

f) The gases were not separated.

g) The gas values are indeterminate due to leaks.

Values of oil shale sample ■ »· ' Remarks fraction Tabel IV Coals water G Sour Stick 2) H / C atom I.
NJ example C. oil material material .. 2.15 ° material material Sweat relationship VO 17th B oil 83.5 11.3 3.3 If 6 fel Ij 62 I. 18th A. • oil Elemental composition 82 _; 8th 11.5 3.6 1.5 0.3; 1.64 21 A. bitumen 83.1 11.3 3.5 0.6 1.63 7-11 A. Oil and. 82.2. 10.1 4.8 V 0.7 1.46 7-11. bitumen 83.1 ⁵ 10 _t 8 ⁵ 3.6 ⁵ v ⁵ 0.5 1.56 ⁵ oil ⁶ W. cn . - Kerogen 84.9 ⁶ 11.3 ⁶ - ■ 1.8 ' 1.60 ⁶ ο rawer 80.5 ⁶ 10.3 ° 5.8 ' 2.4 " 0.83 ⁶ 1.54 ° 985 ——— Slate ⁶ G 1.0 ' ο. —— 16 _; 5 ° O _? 5 ⁶ O ₇ 8 ⁶ 1/56 ο -4 ο
en

1) The samples correspond to the letters listed in Table I.

2)% by weight of the fraction.

3) The combined bitumen fractions of Examples 7 to 11.. '

4) The combined oil and bitumen fractions of Examples 7-11

5) Certain combination of the composition of the elements that one individually in found the oil and bitumen fractions. .

6) Published by M.T. Atwood, Chemtech, October 1973, pages 617-621.

The use of a catalyst in Example 36 causes a substantial increase in the amount of oil fraction formed, relative to the amount of bitumen fraction formed and a decrease in the sulfur content of the products. The use of a catalyst in Example 37 also causes a substantial increase in the amount of the oil fraction formed relatively to the amount of bitumen fraction formed.

The results of the elemental analysis of various samples Oil and bitumen fractions obtained in several of these examples and also from oil shale used as the feed smaterial is used, and oil kerf product that obtained under thermal distillation, M.T. Atwood in Chemtech, Oct. 1973, pages 617-621. These values are listed in Table IV. These results show that the elemental analyzes of the oils from different Oil shales are quite similar. The determined combined results of the oil and bitumen fractions of the examples 7-11, obtained using the process of the invention, show that these pooled fractions have a similar nitrogen content, but a lower sulfur content than the oil that is used in the thermal Receives distillation. The h / C atomic ratio for the Oils obtained using the inventive method are similar to the H / c atomic ratios for the oils obtained from thermal distillation. However, the H / C atomic ratio for the combined oil and Bitumen fractions obtained using the inventive This process receives less than that for the oil, i.e. the total liquid products that are obtained from thermal distillation receives. This can mean a greater overall liquid yield, which is obtained in the process according to the invention obtained compared to thermolytic distillation.

The properties of the combined oil fractions that can be found in Examples 7-11 are determined and the results are shown in Table V along with the comparable ones results described in the literature for

509850/0705

Oil fractions obtained from oil shale by thermal distillation and gas combustion distillation. The olefin content of the oil fraction which boils up to 2O7 ° C (405 ° F) and which is obtained by the process of the invention differs from the olefin content of the oil fractions which are up to. 207 ° C (405 ⁰ F) boil obtained from the gas combustion distillation process and thermal distillation. The olefin content of this fraction obtained in the process of the invention is approximately half that obtained in the corresponding fraction in the thermal and gas combustion distillation processes. Although olefins are the main products in the boiling fractions obtained from thermal or gas combustion distillation of hydrocarbons, oils with reduced olefin content are obtained in the process of the invention. This shows that hydrogen is formed in situ in the process according to the invention and that this hydrogen is at least partially consumed in the hydrogenation of the olefins obtained.

6098SO / 070

Components

.Table V

Composition "*" 'of the liquid form

Thermal gas burning invention distillation style. according to procedure ^ ' ! ation ^)

Bitumen fraction 38

Oil fraction 62

.Acid in the components 3

Base in components 14

neutral oil 45

3 8

up to 2O7 ° C (405 ⁰ F)

15th

20.0 ³
31, 's ³

35.5 ³
24.0 ³
4O ₁ S ³

6 ■
23

²⁷ 3

48 ³

25 ³

Paraffins and

Naphthenes

Olefins

aromatic conn.

'2O7-316 ° C (4O5-6OO ° F)

Paraffins and
Naphthenes
'Olefins
aromatic compounds

316-371 ° C (600-70O ⁰ F) residue [above 371 ° C

(371 ⁰ F)] · - ■ _-.-. "

Remarks . ·

1)% by weight of liquid products, unless otherwise stated.

2) The results are reported by G.O. Dinneen, R.A. Van meter, J.R. Smith, C.W. Bailey, G.L. Cook, CS. Allbright and J.S. Ball in Bulletin 593, U.S. Bureau of Mines, 1961.

3) Volume% of the fraction with a particular boiling point.

50985G / 0705

It has been found that a certain relationship between the volumetrisehen content of hydrocarbons in the oil shale sample and the weight content of hydrocarbons in such samples with the weight loss of such samples during the calcination in air at 538 ⁰ C (IOOO ⁰ F) is for 30 minutes. Both the volumetric and weight contents of the hydrocarbons are determined by the Fischer method described by L. Goodfellow, CF. Haberman and MT Atwood as "Modified Fischer Procedure", Division of Petroleum Chemistry, Abstracts, p. F.86, American Chemical Society, San Francisco Meeting, April 2-5, 1968. This relationship is shown in FIG. 1.

Using this relationship, the expected yield of hydrocarbons from the oil shale samples used is calculated estimated to be the actual hydrocarbon yield with the expected total possible hydrocarbon yield from the oil shale sample used. The weight loss during the calcination of the oil shale samples and the relationship shown in Fig. 1, shows that the oil shale samples used had liquid products in the range of approximately 14 to 22% by weight based on the oil shale product used as a raw material.

The actual weight loss during the calcination of Oil Shale Sample A, the expected hydrocarbon yield with this "oil shale sample and the actual yields of oil, bitumen and gas products (carbon dioxide and C to Co hydrocarbons), the 2-hour batch tests of the oil shale of sample A at various Temperatures obtained are indicated in FIG. These experiments were carried out using slate-water weight ratios of 0.56 or 1 performed. When the ratio was 0.56, 90 g of water was charged. When the relationship 1, 60 g of water was added. The pressure ranged between 179 atmospheres and 295 atmospheres (2550 and 4200 psig). the Values shown in Fig. 2 were taken from the results obtained in Table III. The liquid selectivity,

S098S0 / 0705

the ratio of the total yield of liquid products to the weight loss of the oil shale sample during calcination, for oil shale sample A at 400 ° C (752 ° F) is 0.67. The oil selectivity, the ratio of the yield of oil to the total yield of liquid products, for oil shale sample A at 400 ° C (752 ° F) is 0.61.

The yield of oil obtained from the oil shale depends strongly on the temperature in the process according to the invention. The yield of total liquid product - oil plus bitumen, is roughly constant at temperatures above 401.5 ° C (705 ° F) and drops sharply at temperatures below 401.5 ° C (705 ° F). At temperatures above 401.5 ° C (705 ° F), the total yield of liquid product is the amount that can be recovered, as determined by the Fischer experiment, or is slightly higher. Although essentially all of the available hydrocarbons are removed from the oil shale by the process of the present invention at a temperature of at least 401.5 ° C (705 ° F), the amount of lighter hydrocarbon fractions that are recovered continuously increases as temperatures rise increased above 401.5 ° C (7O5 ° F). This is evident from Fig. 2 by the sharp increase in oil yield when the temperature is above 4O1,5 ° C (705 ⁰ F) is increased forth. Such an increase in oil yield and a decrease in bitumen yield is obvious when cracking of the bitumen occurs - either thermally or catalytically by the presence of catalysts inherently present in the oil shale.

Similar results, shown in Table VI, are obtained for Examples 1, 2, 15 and 26-28 at different contact times and with oil shale samples of different particle sizes than were used to determine the results of FIG. These results show that even at a temperature of 371 ⁰ C (698 ° F) some oil selectivities are significantly reduced below the critical temperature of water, the liquid and compared with the values obtained at temperatures above the critical temperature of water receives.

S098S0 / 07O5

Oil slide
test ¹ ) Tabel (660) VI Fluid
keitsse
selectivity Oil-
selective
vity Values of
example A. Reaction
temperature
OC ( ⁶ F) (752) Reacti
on time
hours 0.27 0.06 2 A. 349 (716) 2 0.67 0.61 1 B. 400 (752) 2 0.63 0.41 28 B. 380 (698) 2 0.58 0.68 15th D. 400 (752) 2 0.42. 0.47 27 D. 371 0.5 0.58 0.50 26th 400 0.5

1) The samples correspond to the letters given in Table I.

6Q98S0 / Q7Q5

The results obtained by using the influence of the Particle size of the oil shale substrate on the speed The extraction of hydrocarbons from oil shale investigated are shown in FIGS. 3 and 4. The graphic Representations of Figures 3 and 4 are obtained using the results of Table III in experiments where a slate-to-water weight ratio of 0.56 is used. The weight loss during CaI-cinierung, the expected hydrocarbon yield from the oil shale sample and the measured liquid yield Hydrocarbon Products - all are in percent by weight on the oil shale feedstock, are expressed in Figure 3 as a function of contact time and area the particle sizes of the oil shale feedstock. In general, oil shale feedstock having a particle size of about 0.6 cm (1/4 inch) Diameter or less than 90% by weight of the carbon content of the oil shale feedstock in less won than 1/2 hour. When the oil shale feedstock has a particle size equal to or less than 2.38 mm (8 mesh), the yield is total liquid Products greater after a contact time of 1/2 hour than after a contact time of 2 hours and exceeds the expected yield of hydrocarbons from the oil shale. With such a feed material corresponds the decrease in the overall yield of liquid hydrocarbon products with increasing contact time of increased conversion the liquid products to dry gas, for example by splitting the liquid products. The split will just go through the graph shown in Fig. 4, where the oil selectivity as a function of the contact time and the area of the Particle sizes of the oil shale feed is shown.

When the oil shale feedstock has a particle size in the range of 0.6 to 0.3 cm (1/4 to 1/8 of an inch), the recovery rate is low enough that the overall yield of liquid products after a contact time of 1/2 hour is less than the total yield of liquid products

509850/070 5

after a contact time of 2 hours. This is evident from FIG. 3 emerged. Although no theory is suggested, if the oil shale feedstock is made from coarser Larger particle size materials exist, the ratio of surface area to particle volume for such materials lower than with finer materials, and the diffusion of water into the coarser oil shale particles * and the rate of dissolution of the inorganic matrix in the supercritical water may decrease, and thus may the recovery rate can be decreased.

There is evidence that the effective recovery of fluids from oil shale according to the invention Process a partial dissolution of the inorganic matrix of the oil shale substrate. After all fluids have been recovered from the oil shale feedstock with particle sizes ranging from 0.6 to 0.177 mm (1/4 inch to 80 mesh) the oil shale solids will be consumed obtained, and they have a much smaller particle size, generally less than 0.149 mm (100 mesh). Furthermore, the bulk density increases from approximately 2.1 g per ml of the loading material to approximately 1.1 g per ml for the solids consumed. On the other hand, if the fluids are not completely out of the oil shale feedstock are recovered, the oil shale particles retain much of their original shape. For example there are minor apparent changes in oil shale feedstock when only half of the carbonaceous material is removed from it.

There is an additional indication of the decomposition of the inorganic matrix of the oil shale substrate during the recovery of the liquid hydrocarbons after the process according to the invention. The high yield of carbon dioxide in extracting the liquid hydrocarbons from oil shale, even at a relatively low temperature of 349 C (66O ⁰ F), indicates decomposition of the inorganic carbonate in the structure of the oil shale. The approximate mass

S098S0 / 0705

balance of the oil shale feedstock and the combined products from the manufacturing processes of the examples 7 to 11 of the liquid hydrocarbons from -the oil slope Test A shows that carbon dioxide is formed from inorganic carbonate, see Table VII.

Table VII component Symbol of % By weight, be Constituent moved to that Oil shale Loading mat. Kerogen loading Titratable with acid ^K C inorganic carbonate 32 Inorganic solid, ¹ C exclusively with acid S. 19th titratable inorganic 49 cal carbonate

total

100

Recovered products

Dry gas
Oil and bitumen
Carbon oxide
Kerogen coke

Inorganic carbonate that can be titrated with acid

Inorganic solid, only inorganic that can be titrated with acid Carbonate

total

IF

23 7 4

15 50

100

6098 SO / 0705

The relationships by which the products are denoted are given below. The total amount, S _Q , of the oil shale feed smaterialε, excluding the trapped water, is given as follows:

S ₀ - s + i _c + k _c ,

where the symbols used are defined in Table VII.

When the oil shale feedstock is titrating with acid becomes, the amount of acid titratable inorganic carbonate originally present becomes I "in the oil shale feedstock determined, and thus the relationship between the measured amount of acid titratable inorganic carbonate initially present and the total measured amount of oil shale feedstock will. This relationship for the oil shale material of Sample A is:

I _c = 0.187 S ₀

If the oil shale feed material is calcined in air for 30 minutes at 538 ° C (1000 ⁰ F), all organic material is discharged, and the specific weight of the entire inorganic material can be expressed as the total amount of oil shale feed material as follows:

S + I _c = 0.678 S ₀

From the last two equations, S can be calculated. It is 0.491 S _Q.

The solid products that are found in the extraction of hydrocarbons obtained from the oil shale feed material by the process of the invention are given as follows:

S + xl _c + yK _c = 0.686 S _Q ,

S098S0 / 070S

wherein the symbols used are defined in Table VII. The conditions used in this experiment are temperature of 400 ° C (752 ° F), a pressure of about 281 atmospheres (4000 psig), a time of 2 hours, an addition of water of 60 g and a slate-to-water weight ratio of 1.0 «

When the spent solid oil shale residue is titrated with acid, the amount of acid-titratable inorganic carbonate present in the spent solid after the experiment and the relationship between the measured amount of acid-titratable inorganic carbonate after the experiment can be determined the removal of hydrocarbons is present, xl _c , and the measured total amount of oil shale can be expressed as follows:

xl _c = 0.147 S ₀ ,

where χ denotes the part of the amount which is originally present and I _c denotes the part which still remains.

When the spent oil shale solid in air 30 minutes is calcined at 538 ° C (1000 ° F), all organic materials are driven out, and the determined weight of the total organic materials remaining after removal of the hydrocarbons, based on the total amount of the oil shale, can be expressed as follows:

S + xl _c = 0.643 S ₀

From the last two equations, S is calculated. It is 0.496 S _Q. This value closely corresponds to the value of S as calculated from the analytical properties of the oil shale feedstock.

A very important result of the analytical characterization, that is listed in Table VII is that the amount of acid titratable inorganic carbonate in the solid used oil shale is much lower than

S0985 0 / Ö7Q5

the amount of acid-titratable inorganic carbonate in the oil shale feedstock and that the difference between these amounts corresponds to between 50 to 60% by weight of the gaseous carbon dioxide formed. That Carbon dioxide from the kerogen in the oil shale feedstock originates from, could correspond to part of the rest. In general, the inorganic carbonate in The structure of the oil shale can withstand thermal treatment if the temperature does not exceed 538 ° C (1000 ° F) is. The thermal or gas combustion distillation thus usually does not reduce the amount of acid titratable inorganic carbonate. On the other hand, in the method according to the invention, the amount of acid is titrated. Inorganic carbonate in the structure of the oil shale is reduced.

The results of 2 hour batch runs at 400 ° C (752 ° F) are reported in Table VIII, and they show the effect of the weight ratio of oil shale charge to solvents on the total yield of liquid products and on the oil selective! The extraction is complete at the conditions used when the weight ratio of oil shale feedstock increases Solvent ranges from about 1: 1 to about 1: 2. A weight ratio in this range also allows the transition of the fluid material and the compression of the oil shale feed solvent mixture so that a continuous slurry treatment system is possible will.

6098S0 / 0705

• Η O, β W .Q-H

- 42 -

Table VIII

oil
slate
sample ^ - ' Oil shale
to water-
Weight
relationship Expected
Total carbon
spring water
s toff yield Weight
on
Mat. -%, based
the loading. "
, won as A. 1.0 22nd oil bitumen A. 0.6 22nd 13.2 8.3 1.0 16 13.5 6.5 B. 0.6 16 11.8 9.0 C. 1.0 22nd 10.5 5.0 C. 0.6 22nd 17.8 9.2 14.4

1) The samples correspond to those given in Table I. Letters. . "

S09B50 / Ö705

Example 38 turns off hydrocarbons. Raw tar sand obtained batchwise using the method according to the invention. The following conditions are used: a reaction temperature of 400 ° C (752 ° F), a reaction time of 2 hours, a reaction pressure of 288 atmospheres (4100 psig), and 17.6 atmospheres (250 psig) argon pressure. The feed material consists of 40 g of raw tar sand in 90 g of water. This The experiment is carried out in a 300 tnl Hastelloy alloy C Magne-Drive autoclave carried out. The products obtained from this experiment are gas (hydrogen, carbon dioxide and Methane) and oil in amounts corresponding to 2 and 8% by weight, based on the feed material. The oil is API-specific Weight of about 17.0 and sulfur, nickel and vanadium contents of 2.7% by weight and 45 and 30 ppm, respectively. On the other hand, tar sand oil has been produced by the COFCAW process is obtained, an API-specific weight of 12.2 and sulfur, nickel and vanadium contents of 4.6% by weight and 74 and 182 ppm, respectively. Thus, the quality of the according to the invention Process obtained oil better compared to the oil produced by the COFCAW process.

The yields of gas, oil, bitumen and solid products in this example are 2.5, 3.7, 3.4 and 86.5% by weight, based on the tar sand feed material. This means that the hydrocarbon content is almost completely recovered of the tar sand feed material. The total amount of gas, oil, bitumen and solid fractions and of water that is 97.4% by weight based on the tar sand and the water, i.e. the feed materials.

Examples 39 to 192

Examples 39-192 are run on a batch basis and use various types of hydrocarbon feedstocks under inventive conditions implemented. In these examples it is explained that an effective cleavage in the process according to the invention. Desulfurization and, if the carbonaceous material is oil

SOS 85 0/0705

slate or tar sand solid or a hydrocarbon fraction is the paraffins, olefins, olefin equivalents or Contains acetylenes as such or as substituents on ring compounds, a demetallization and optionally a Hydrogenation and denitrification of the hydrocarbons takes place and that therefore the process according to the invention obtained hydrocarbons from the oil shale, tar sands or Carbon solids split, hydrogenated, desulphurised, demetallised and are cleared of nitrogen. Unless otherwise specified, the following procedure will be used in each case carried out. The hydrocarbon feedstock, the water-containing fluid material, and the components of the catalyst system, if present, are converted into a Hastelloy alloy C Magne-Drive- or Hastelloy alloy B Magne-Drive autoclave in which the reaction mixture is mixed. The components of the catalyst system are found as solutes in the fluid material that contains water or as solids in slurries in the fluid material containing water added. Unless otherwise stated, there is sufficient water in each Example added so that at the reaction temperature used and at the reaction volume used, the density of the water is at least 0.1 g per ml.

The autoclave is flushed with inert gas, namely argon, and then closed. This inert gas is also added, to increase the reaction pressure. The proportion of argon to the total pressure at ambient temperature is called the argon pressure designated.

The temperature of the reaction system is then increased to the desired value, and the phase of fluid, dense material which contains water is formed. About 28 minutes are required to heat the autoclave from the ambient temperature 349 ° C (660 ⁰ F). It takes approximately 6 more minutes to increase the temperature from 349 ° C (66O ° F) to 371 C (700 F). It then takes approximately an additional 6 minutes to increase the temperature from 371 ° C (700 ° F) to 399 ° C

5098S0 / 0705

(750 F) to increase. When the desired final temperature is reached the temperature is kept constant for the desired time. This constant end temperature and the duration up to this temperature are called the reaction temperature and response time defined. During the reaction time, the pressure in the reaction system rises as the reaction continues progresses. The pressure at the beginning of the reaction time is defined as the reaction pressure.

After the desired reaction time at the desired reaction temperature and the phase of dense fluid material containing water is relaxed and at the desired pressure while the pressure is released, the reaction vessel is distilled, whereby gas, water-containing, fluid material and "light" Ends are removed and "heavy" ends, catalyst, if any, and other solids in the reaction vessel lag behind. The "light" ends are liquid hydrocarbon fractions, which boil at or below the reaction temperature, and the "heavy" ends are hydrocarbon fractions, which boil above the reaction temperature.

The gas, the water containing fluid material and the light ends are in a pressure vessel filled with liquid Nitrogen is cooled, collected. The gas is removed by heating the pressure vessel to room temperature and then analyzed by mass spectroscopy, gas chromatography and infrared spectroscopy. The containing water Phase and the light ends are then removed from the reaction vessel with compressed gas and occasional heating of the Kessel driven out. Then the fluid containing water and the light ends are decanted separated. Alternatively, this separation process can take up to one postponed to a later stage in the process. Gas chromatograms of the light ends are determined.

509850/0705

The heavy ends and solids, including the catalyst, if present, are washed out of the reaction vessel with chloroform, and the heavy ends are dissolved in this solvent. The solids, including the catalyst, if any, will be then separated from the solution containing heavy ends by filtration.

After the chloroform is separated from the heavy ends by distillation, the light ends and the heavy ends become mixed. If the water-containing fluid material has not been severed from the light ends, then it will separated from the combined light and heavy ends by centrifugation and decantation. The United Light and heavy ends are based on their nickel, vanadium and sulfur content, carbon-hydrogen atomic ratio (c / h) is analyzed and the API specific gravity is measured. The water is analyzed for nickel and vanadium, and the solids are analyzed for nickel, vanadium and sulfur. X-ray fluorescence was used to scrap nickel, vanadium and sulfur.

Examples 39 to 41 illustrate that the in the invention Process catalysts used are not poisoned by sulfur-containing compounds. Three attempts were performed each with carbon monoxide at 27.6 atmospheres (350 psig) in 90 ml of water in a 240 ml Magne-Dash autoclave during a reaction time of 4 hours. Soluble ruthenium trichloride in the amount of 0.1 g RuCl-J * 1-3HpO was used as the catalyst in these examples used. In addition, in Example 40, the water contained 1 ml of thiophene. The reaction conditions and the compositions the products in each experiment are given in Table IX. The presence of a sulfur-containing compound, Thiophene, did not poison the catalyst or inhibit water-gas rearrangement.

509850/0705

Table IX

At-reaction-reaction product composition

game
No. temperature
O / - f Op ) pressure ^l J
atü (psig) ^H 2 co ₂ CO 39 354 (670) 176 (2500) 39 32 29 40 350 (662) 176 (2500) 25th 23 52 41 350 (662) 179 (2550) 26th 22nd 52 Remarks

1) atü (psig)

2) Normalized mole percent of gas.

Example 42 illustrates that the catalyst system acts as a catalyst for the hydrogenation of unsaturated organic compounds. When 15 g of 1-octene is mixed with 30 g of water in a 100 ml Magne-Dash autoclave for 7 hours at a temperature of 350 ° C (662 ° F), a reaction pressure of 246 atm (3500 psig) and an argon pressure of 56.2 atmospheres (800 psig) are treated in the presence of soluble RuCl ₃ * l-3HpO catalyst, the analysis of the products provides carbon dioxide, hydrogen, methane, octane, cis- and trans-2-octene and paraffins and Olefins containing 5, 6 and 7 carbon atoms, solid. These products indicate that there is substantial skeletal cracking and isomerization and localization of the sites of unsaturation. A 40% yield of octane is obtained when 15 g of 1-octene and 30 g of water in the presence of 0.1 g of RuCl ₃ '1-3H ₂ O for 3 hours in the same reactor and at the same temperature a reaction pressure of 174 atmospheres (2480 psig) and an argon pressure of 19.1 atmospheres (200 psig). A 75% yield of octane is obtained from the reaction mixture in the same reactor and under the same conditions, but after a reaction time of 7 hours and at a reaction pressure of 244 atmospheres (34-70 psig) and an argon pressure of 56.2 atmospheres. 800 psig).

S098S0 / Ö705 '

Examples 43 to 44 relate to experiments in which sulfur-containing compounds, for example thiophene and Benzothiophene, to hydrocarbons, carbon dioxide and elemental Sulfur are decomposed. These examples illustrate the effectiveness of the catalyst system in catalysis Desulfurization of sulfur-containing organic compounds.

In Example 43, a reaction mixture of 12 ml of thiophene and 90 ml of water is used in a 240 ml Magne-Dash autoclave in the presence of 0.1 g of soluble RuCIo · l-SPL ^ O catalyst at a reaction temperature of 350 ° C (662 F) and a reaction pressure of 221 atmospheres (3150 psig) and an argon pressure of 45.7 atmospheres (650 psig) and reacted for a reaction time of 4 hours, one C ^, - to C. hydrocarbons and 0.1g solid elemental sulfur, but none detectable Amounts of sulfur oxides. Or hydrogen sulfide is obtained.

In Example 44, a mixture of 23 ml of a solution of 8 mol% thiophene (ie approximately 3% by weight sulfur) in 1-hexene and 90 ml of water is made in a 240 ml Magne-Dash autoclave in the presence of 2 g of solid Alumina support containing 5% by weight ruthenium (equivalent to 0.1 g RuCl ₃ * 1-3H ₂ O) at a reaction temperature of 350 ° C (662 ° F), a reaction pressure of 246 atm (3500 psig) and an argon pressure of 42.2 atmospheres (600 psig) and for a reaction time of 4 hours to give hydrocarbon products containing sulfur in an amount of 0.9% by weight based on the hydrocarbon feed in the form of thiophene . This decrease in thiophene concentration corresponds to 70% desulfurization. The activity of the catalyst does not deteriorate during 4 successive batches.

Examples 45 to 52 process samples from vacuum gas oil and residual fuels, and these examples explain that the catalyst system does the desulfurization, demetal-

5 0 9 8 5 0/0705

lization, splitting and quality improvement of hydrocarbon fractions effectively catalyzed. The composition of the hydrocarbon feedstocks used are given in Table X. The residual oils used in these examples are shown in Table X by expressed the letter "A".

Examples 45 to 48 relate to vacuum gas oil, Examples 49 to 50 relate to C atmosphere residual oil, and Examples 51 to 52 relate to Kafji residual oil. Example 45 relates to vacuum gas oil under conditions similar to those used in Examples 46 through 48, but in the absence of a catalyst, and is listed for comparison with. The experimental conditions, product compositions and the extent of sulfur, nickel and vanadium removal in these examples are given in Table XI. The liquid products are characterized by the fact that they boil lower or higher, depending on whether they boil at or below the reaction temperature. The reaction temperature is 379 C (715 ° F), and in each. For example, a 300 ml Hastelloy alloy B Magne-Dash autoclave is used. Ruthenium, rhodium and osmium are added in the form of soluble RuCl ^. 1-3HpO, RhCl ₃ * 3HpO or OsClo * 3H "0. The percentage of sulfur, nickel and vanadium removed is reported as the percentage of sulfur, nickel and vanadium removed from the product based on the hydrocarbon feed.

509850 / 07OS

cn

(D OD on

cn

«D

f-

Atmosphere
Residual oils A Khatjx Table X Atmospheric
, Residual oils B 3.89 C. Cyrus C vacuum 4 _; 64 C. S3 Tar sand oils distillation) Khaf ji 93 3.44 5.45 Residual oil 54 Vacuum- 3.6 84 Straight topped
(bd er st en (bd after s t. 5.17 31 25th 175 34 Analysis of gas oil 30th 30th Distillate. \ 275 84.47 16 59 84.88 Sulfur U 2 _; 56 14th 4.56 104 10.99 * 85.04 84.25 10 _r 08 2)
Vanadium 182 82.39 Ij56 11.08 10.20 ' '1.43 Nickel ² > 74 9.99 14.8 1.56 1.45 5.4 Carbon ¹ ^ 83.72 1.455 10.6 15.4 9.8 Hydrogen 1) 15th 10.56 7.1 12.0 6.9 h / c atomic ratio 15th Remark 1.514 V API specific weight ³⁾ . 1
2
3 12.2 Faction under
343 ° C (6 50 ° F) boils 15 29.4 Weight%
ppm
⁰ API

Ul

cn

. NJ

CO

CO

■. Table XI ".""· -. ■

Example Example Example Example Example Example Example example

45 46 47 48 49 50 51 52

Reaction ^pressure} 190 (2700) 162 (2300) 246 (3500) 260 (3700) 257 (3650) 265 (3775) 255 (3630) 257 (3650)

Argon Pressure ¹ ^ "450 (31.6) 450 (3 ^ 6) 300 (21.1) 450 (31.6) 400 (28.1) 450 (3.1.6) 400 (28.1) 400 (28.1) )

Response time 2) 7 g 5 2 16 16 13 13

Oil to water weight ratio

^{m added} water ^)

* ° catalyst
co

Catalyst concentration ^ '

^ö 'Product composition 5)

ο gas

c / 1 low boiling point
liquid

higher boiling liquid

Sulfur content ⁶ ^

Nickel content ⁶⁾ , 7)

Vanadium content ⁶⁾ » ⁷ ^
% Sulfur removal
% Nickel removal
% Vanadium removal

5.4 3 8th - 6th 0.2 0.3 \ - 0.3 0.3 0.3 0.3 20th 49 20th . 96 90 20th 96 96 96 96 none 48 Ru Ru Cs + Rh Ru Os Ru Os - 2.36 0.03 '0.04 0.07+
0.03 0.03 0.09 0.03 0.09
t - 4th 11 21 12th 22nd 10 10 ' 46 79 79 50 - 22nd 30th 50 10 0 32 - 68 51 2 _r 25 h ⁹⁷ 2.08 2.0 2,, 6 2.8 3.4 ■; - - 9 • - 10 2 - - 6th . - 16 9 12th 23 48 28 34 20th - - 36 ·
80. 67
81 93 CJI
kj
89 IS3
CO

Table XI (continued) Comments

1) atü (psig)

2 hours

3) g
cn

ö 4) The amount of catalyst added is expressed in g and

go in the same order in which the corresponding catalogs

Q lysers specified are listed.

O 5)% by weight of the hydrocarbon feed,

_ö unless otherwise stated.

6) Obtained from analysis of pooled liquid fractions.

7) ppm

KJ K) LO

A comparison of the results from Table XI shows that with the same thermal processing without the addition of catalyst from an external source, a considerable crack and quality improvement and little desulfurization the hydrocarbon fraction is achieved. With a relatively high oil-to-water weight ratio are the compositions of the products obtained during thermal processing and during processing in the presence a ruthenium catalyst obtained similarly. In the case of a low oil-to-water weight ratio, the analysis of the Products cause greater cleavage in the presence of a ruthenium catalyst. In similar conditions and with a Ruthenium or a rhodium-osmium mixed catalyst occurs essentially a complete conversion of the liquid Feed material in gases and liquid products at temperatures equal to or below the reaction temperature boil. The sulfur that is removed by desulfurization is in the form of elemental sulfur when the water density is at least 0.1 g per ml, for example when the oil-to-water weight ratio is 0.2 or 0.3 amounts to. However, the removed sulfur is in the form of hydrogen sulfide if the water density is less than 0.1 g per ml, for example when the oil-to-water weight ratio 5.4 or 6. This clearly shows a change in the mechanism of desulfurization of organic Compounds when treated with a dense, water-containing phase, depending on the density of the dense, Phase containing water.

In Examples 53 to 54, activators or accelerators are used used for the catalyst system of the invention. Basic metal hydroxides and carbonates and transition metal oxides, preferred oxides of metals of groups IVB, VB, VIB and VIIB of the Periodic Table, do not act as Catalysts in the water reforming process, but they do effectively increase the activity of the catalysts according to the invention, which catalyze the water reforming or conversion.

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The activator or accelerator can be as a solid or slurried in the reaction mixture or as a water-soluble one Salt, for example as manganese chloride or potassium permanganate, which is the corresponding oxide among those used in the process according to the invention Forms conditions. Alternatively, the activator can be deposited on a carrier and as such in a Fluidized bed configuration can be used, or it can be slurried in the fluid material containing water will. The ratio of the number of atoms of metal in the activator to the number of atoms of metal in the catalyst ranges from about 0.5 to about 50, and preferably from about 3 to about 5.

The yields of products in the water reforming process are good indicators of activator activity. In which Water reforming processes become hydrocarbon in situ and carbon monoxide by reacting a portion of the hydrocarbon feed formed with water. The carbon monoxide formed reacts with water and forms carbon dioxide and additional hydrogen in situ. The hydrogen so formed then reacts with a portion of the hydrocarbon feed from the saturated materials. In addition, some of the hydrocarbon can hydrocrack and form methane. The yields of saturated product, carbon dioxide and methane are good measures for the activator activity, when an activator is present in the catalyst system.

The yields of hexane obtained when 1-hexene is processed in Examples 53 and 54 are shown in FIGS. 5 and 6 shown. The hexane yield is expressed as mol% based on the feedstock, the 1-hexene, is indicated which is converted to hexane in the product.

Examples 53 and 54 have a reaction temperature of 350 ° C (662 ° F), a reaction time of 2 hours, 90 g Water, 17 ί 0.5 g 1-hexene and a 300 ml Hastelloy alloy B Magne-Dash autoclave used. For Fig. 5 the

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seek at which the points labeled 1 through 5 are obtained at reaction pressures of 242.5, 239, 197, 242.5 and 246 atmospheres (3450, 3400, 2800, 3450 and 3500 psig, respectively) and argon pressures of 45.7, 45.7, 0, 43.6 and 43.6 atmospheres, respectively (650, 650, 0, 620 and 620 psig, respectively). In the attempts corresponding to the points marked 1 to 3, 0.2 g of manganese dioxide is used as an activator, whereas no activator was used in the tests corresponding to points 4 and 5. In Fig. 6 For the tests in which the points labeled 1 to 3 are obtained, reaction pressures of 197, 250 were obtained and 204 atmospheres (2800, 3560 and 2900 psig, respectively) and argon pressures of 45.7 atmospheres (650 psig) were used.

It can be seen from FIG. 5 that the hexane yield increases with increasing amounts of ruthenium catalyst and with either no added activator or with 0.2 g of added manganese dioxide as the activator. Similarly, FIG. 6 shows that an increase in the hexane yield occurs with increasing amounts of manganese dioxide activator and 0.1 g of RuCl ₃ * 3H ₂ O catalyst present. These graphs show that in the absence of catalyst the activator alone does not exhibit catalytic water reforming activity, the hexane yield is less than 2 mole percent based on the feed. For a given concentration of catalyst, an addition of 0.2 g of activator results in a substantially increased yield of hexane in the product.

In Examples 55 to 68, 2-hour approaches are carried out in a 300 ml Hastelloy alloy B-Magne-Dash autoclave, and 0.1 g of RuCl ₃ «ISO catalyst and 0.2 g of various Transition metal oxides used at 350 ° C (662 ° F). The argon pressure is 45.7 atmospheres (650 psig) in each example. The yields of hexane, carbon dioxide and methane are given in Table XII.

509850/0705

cn ο

²
"0

m
O

At-

game

56 57 58

59

60

61

62

63

64

65

66 ■

67

68

Activator

V ₂ O

₅ .

Cr ₂ O ₃ MnO ₂

Fe ₂ O ₃ TiO ₂

MoO ₃

CuO

BaO

ZrO ₂

Nb ₂ O ₅

Ta ₂ O ₅

ReO ₂

WOo

Φ water Table XII (2900) • • 88.8 1)
Reaction - Composition of the
Be s chi ckunq smaberials 90.9 pressure 2; (3325) Hexane 3) 1 witches 89.8 204 (3500) 25th 17.8 9OjO - 39 16.4 . 88.7 234 - 32 16.6 89.1 246 >. (3450) 57 16.9 89.5 - 37 15.9 89.8 i (3250) 30th 16.5 9OjO 24 2.5 (3600) 30th 16.4 90.1 (3000) 17th "16.2 90 _T 5 228.5 (3850) 2 16.3 75.8 253 - 27 16.4 89.2 211 -. 26th 16.5 90.6 271 27 12.5 27 16.4 33 17.6 Remarks

Carbon dioxide ⁴ )

0.04

0.07 0.07 0.05

0.09 0.05

0.065 0.025

0.08

0.068

0.038

0.01

0.053

2) atü (psig) ' _: . ·. · "

3) Mol% based on the hydrocarbon feed

4) moles ■ '' · ■ "■■

methane

^4>

0.03

0.04 0 _t 02 0.06

0.03 0 _; 03

0.06

- <n

0.011 0.010

0.007

0.009

• 3-: · ■■

approx

There is an increase in the yield of hexane with all oxides that are used, except for barium oxide. There is only a slight increase in the yield of hexane when copper (II) oxide is used. The shown activators thus effectively activate the catalytic activity in water reforming, and are particularly effective Transition metal oxides.

The ratio of the yield of methane in moles to either the yield of carbon dioxide in moles or to the yield of hexane in mol% based on the hydrocarbon feed material, is an indication of the relative extent to which the competing hydrocracking reactions and in situ hydrogen formation take place during water reforming. The results shown in Table XII show that a given activator activates the hydrocracking and the hydrogen formation to different extents. It is therefore by choosing an activator compared to another, possible, either selective hydrocracking or hydrogen formation to favor and also to increase the activity of the catalyst.

No theory is to be suggested as to the mechanism by which the basic metal hydroxides and carbonates and transition metal oxides enhance the activity of the catalysts in the process of the invention. However, there is evidence that the increase in catalytic activity by the transition metal oxides is at least a chemical effect and not a surface effect. By way of illustration it should be stated that Example 68 was carried out under the same experimental conditions as were used in Example 55, but that 1 g of activated carbon chips with a high surface area, containing 5% by weight of ruthenium - ie 0.5 mmol of ruthenium, was used instead as a catalyst , which is equivalent to 0.1 g RuCl ₃ * 1.3H ₂ O - were used and that no activator was present. The coal chips

2 (chunks) had a surface area of 500 m per g.

509850/0705

252231a

The yield of hexane is 12 mol% and the yield of Carbon dioxide is 0.017 mole. Both of these yields are less than the corresponding yields found in. Example 55 received in the absence of an activator.

In Examples 70 to 76, it is explained that various Effectiveness of the various combinations of catalysts and activators in catalytic cracking, the Hydrogenation, skeletal isomerization, and olefin-positional isomerization of the hydrocarbon feed. In each example, the feedstock is hydrocarbon a solution of 36 mol% 1-hexene in dilute benzene, with the exception of Example 74, in which the benzene is replaced by ethylbenzene. In each example, the reaction is carried out in a 300 ml Hastelloy alloy B Magne Dash autoclave under an argon pressure of 45.7 atmospheres (650 psig), a reaction temperature of 350 ° C (662 ° F) and a reaction time of 2 hours. The compositions of the feed material, the prints, the catalyst compositions, product yields and 1-hexene feed conversions are in Table XIII given.

509850 / 070S

Composition of
Feed hydrocarbon
water

Reaction pressure ²⁾

Catalyst composition D '

RuCl ₃ >> l-3H ₂ O '0 _v 05

Na ρ CO, -

TaCl ₁ - -

TiO, -

3)

Product yields

'Methane. 1

n-pentane 1

·
n-hexane 26

% Conversion based on 97

introduced 1-hexes 3)

· Comments .

Table XIII ·.

Example Example Example Example Example Example Example 70 7J 72_ 73 74 75 76

17 15 17 17 .16

. 91 91 90 91 91 91 91

183 (2600) 239 (3400) 242.5 (3450) 249.5 (3550) 249.5 (3550) 249.5 (3550) 232 (3300)

0.05 0.3 0.2

0.05 0.3

12 71 98

66 97

0 _; 05 0.6

.5 68 97

, 05 5 0.05 4 · 0.05 0.3 7th 0.3 .6 0 _; 3 0.2 87 .0.2 82 - - 98 - 99 0.2 6th 9 • 84 99

D g

2.) atü (psig ·) ■ .. ·. ■

3) mole percent based on I-hexene feed

The high conversion of 1-hexene in Example 70 shows that Skeletal isomerization to methyl pentenes and the olefin-positional isomerization to 2- and 3-hexene, but only a 26% yield of hexane is obtained with the catalyst system without activator. The addition of a transition metal oxide, a transition metal salt, for example tantalum pentachloride, which forms a transition metal oxide under the conditions used, or a basic metal carbonate a substantial increase in the yield of hexane. When the catalyst system is basic, skeletal isomerization occurs completely suppressed, but the olefin position isomerization still occurs. None of the in the Examples 70 to 76 used catalyst systems is effective in the cleavage or hydrogenation of the diluents, Benzene and ethylbenzene. If ethylbenzene is used as a diluent, only trace amounts of dealkylated are used Products, benzene and toluene.

Examples 77 to 83 illustrate the relatively high effectiveness of certain compounds of the catalyst system in the Process according to the invention in the catalysis of the cleavage of Alkyl aromatics. In each example, the hydrocarbon feedstock is a solution of 43 mol% 1-hexane and 57 mol% ethylbenzene used. In each example, the hydrocarbon and water are placed in a 300 ml Hastelloy alloy B Mange Dash autoclave for 2 hours at a reaction temperature of 350 ° C (662 ° F) and under argon pressure of 45.7 atmospheres (650 psig). The composition of the feed, the reaction pressure, the compositions of the catalyst and the product yields are given in Table XIV.

0 9 8 5 0/0705

Table XIV

Composition of the feed ^{material Xl}

Hydrocarbon

water Reaction pressure cn Catalyst- 860 Assemble
RuCl ₃ -1-3H ₂ O cn
O Na ₂ CO ₃ O H ₃ PtCl ₃ O CoCl ₃ cn IrCl ₃ · 3Η ₂ Ο RhCl ₃ -3H ₂ O PdCl ₂ yield . Hexane ^ ' Benzene ⁴ ^ Toluene ⁴⁾

Example Example Example Example Example Example Example 77 78. 79 80 81 82>. 83

16

17 18 17

91 90 90 91 90

225 (3200) 214 (305 "O) 204 (2900) 204 (2900) 186 (2650) 179 (2550)

0.05

0.3 0.1

0.05

0.05
0.3

0.05
0.3

0.1

0.2

0.05 0.3

16

90

179 (2550)

0.05

0.3

0.10

68 0.1 .85 85 • 88 WR 20th 2 47 4th .3 3 58 1 . 1 1 14th 8th 4th 1 1 2 1

Table XIV (continued) Notes

1) g

2) atü (psig)
on

° 3) Made from 1-hexene and expressed as mol%,

eo based on the introduced 1-hexene.

^m .. ι

° 4) Manufactured from ethylbenzene and expressed as mol%,

ο based on alkylbenzene feed. ¹ ^

-i. ι

M KJ GO

Although all of the catalyst systems used in Examples 77-83 are effective in reducing water reforming activity To catalyze, only iridium and rhodium are effective to split ethylbenzene into benzene and toluene. A comparison the product yields in Examples 80 to 82 shows that cleavage of the alkyl aromatics is achieved if uses a catalyst system that is either iridium or rhodium combined with a catalyst according to the invention, but not iridium or rhodium alone.

In Examples 84 to 86 it is explained that alkylbenzenes are cleaved when the process according to the invention is used and the same catalyst system as used in Example 80 was used even in the absence of an olefin in the hydrocarbon feed. Each of these examples is a 2 hour run in a 300 ml Hastelloy alloy B-Magne-Dash reactor at a reaction temperature of 350 ° C (662 ° F) and under an argon pressure of 45.7 atm (650 psig). The compositions of the hydrocarbon feed smaterials, the amount of water added, the reaction pressures and the yields of the products in the cleavage of the alkyl aromatics are given in Table XV.

609850/0705

Example 84

Composition of the • feed material ^ - '

Table XV Ex. 85

Ethylbenzene propylbenzene toluene n-heptane water 2)

Reaction pressure ■

Composition of the product methane benzene

Toluene ethylbenzene ->)

Propylbenzene Remarks

0.15

91 172 (2450)

0.05

0.001 (l%) ⁴

0.018 (12%) '

0.13

0.050

0 _r 12 91 211 (3000)

0.05

0.001 (2%) * 0.007 (14%) ⁴ 0.004 (8%) ⁴

0 _; 039

At sp. 86

0 , 16 , 008 92 , 005 (3%) ⁴ 204 (2900) , 15 0 .001 (0.6%) 0 0 0

1) moles, unless otherwise stated.

2) g

3) atü (psig) ■ ·. .

4) Mol%, based on the feed material, namely the alkyl aromatics in brackets. ■ 5) including xylenes ..,

In Example 87 it is explained that saturated hydrocarbons can be split if one of the invention Procedure using the same catalyst system as used in Example 80. With this one Example are 15.9 g of n-heptane and. 92.4 g of water mixed in a 300 ml Hastelloy alloy B Magne-Dash autoclave, and at a reaction temperature of 350 ° C (662 ° F) under a reaction pressure of 218 atg (3100 psig) and an argon pressure of 45.7 atmospheres (650 psig) for a reaction time of 2 hours. Methane in an amount of 0.67 g, accordingly 4.2% by weight of the n-heptane feed, is formed in the reaction. The fact that only traces on products with a higher carbon number than Methane being found indicates that when a molecule of saturated carbon is broken down, it is completely broken down is split.

Examples 88 through 117 illustrate the processing of tar sands oil feedstock in a 300 ml Hastelloy Alloy C Magne-Drive reactor. The properties of the feedstocks used in these examples, ie tar sands, are given in Table X. "Topped", i.e., distilled tar sand oils, are the tar sand oils of the 1st distillation, the properties of which are given in Table X, but are approximate. 25% by weight light material was removed. 1st distillation tar sand oils (so-called straight tar sand oils) are used as the feedstocks of Examples 88-103, whereas "topped" tar sand oils are used as the feedstocks in Examples 104 to 117. The experimental conditions used and the analytical results of the products obtained are those of these examples in Tables XVI and XVII In all examples the reaction temperature was 400 ° C. (752 ° F.) Ruthenium, rhodium and osmium earth in the form of the soluble salts, namely RuCl ₃ · 1-3HpO, RhCl ₃ * _{Added 3H 2} O and OsCl ₃ -3H ₂ O. Each component of the catalyst system in each example is either in the form of the aqueous solution or as a solid in

509850/0705

added to a slurry of the solid in water, depending whether the component is water soluble or not.

A comparison of the results given in Table XVII shows that the formation of gas and solid residue and the Extent of sulfur and metal removal is increased when the reaction time is increased from 1 to 3 hours and none Catalyst is added from an external source. The addition of a catalyst from an external source gives one slight increase in the yields of solid residue and in the API specific weights of the liquid product, however unlike feedstocks other than tar sand oils, they have little effect on yields in hydrocracking and on the c / H atomic ratios. One Change the oil-to-water weight ratio from 1: 3 to 1: 2 generally gives a decrease in the amount of sulfur and metal removal and an opposite displacement in product distribution. With feed materials other than tar sand oils, shifts are less disadvantageous with increases in the hydrocarbon-to-water weight ratio, until 1: 1 is reached.

The results of the heavier tar sand oils that are already distilled are similar to those of the non-distilled tar sand oils. The only difference is that the conversion of heavy ends to light ends in the tar sand oils that have already been distilled increases further when the reaction time is increased from 1 to 3 hours, with such conversions essentially occurring in about 1 hour in the case of the non-distilled tar sand oils have ended.

The overall yields and compositions of the gas products obtained in a number of examples, their conditions in Table XVII are listed in Table XVIII.

509850/0705

Table XVI

at
game Re-
active
gns i) Reak
functional
pressure 2) 88 6th 320 (4550) 89 6th 327 (4650) 90 2 323 (4600) 91 6th 309 (4400) 92 3 306 (4350) 93 ' 1 306 (4350) 94 3 306 (4350) 95 1 316 (4500) 96 1 311 (4425) 97 2 288 (4100) 98 1 299 (4250)

Argon pressure ^ /

31.6 (450)

31.6 (450) '

31.6 (450)

31.6 (450)

28.1 (400)

28.1 (400)

28.1 (400)

28.1 (400)

28.1 (400)

28.1 (400)

28.1 (400)

Amount of water weight added to oil to water

Water 3) ratio

91
90
90
90
90
90
90
91
90
90
80

1: 3 1: 3 1: 3 1: 3 1: 3 1: 3 1: 3 1: 3 1: 3. 1: 3. 1: 2

Kata
lyser Amount of too
given «V
catalyst Rh + Os 0.15 +0.14 Ru 0.15 Ru 0.15

Rh + Os Rh + Os Ru + 0s

Ru + 0s

0.15 +0.14 0.15 + J, 14 0.15 +0.14 0.10 + 0.10

0.15 +0.20 Na

Table XVI '(continued)

At-'
game Re-.
active
gns -i ) Reak
functional
pressure 2) argon
pressure *) 99 1 ■ 299 (4250) 28.1 (400) cn
ο 100 1 306 (4350) 28.1 (400) co
co 101 2 295 (4200) 2 8.1 (400) crt
O 102 2 295 (4200) ? 8.1 (400) ******
O
"4 103 1 302 (4300) 28.1 (400) O
cn 104 1 302 (4300) 28.1 (400) 105 3 302 (4300) 28.1 (400) 106 3 302 (4300) 28.1 (400) 107 1 306 (4350). . 28.1 (400) 108 1" 313 (4450) 28.1 (400) 109 2 292 (4150) 28.1 (400). 110 2 299 (4250) 28.1 (400)

Amount of water weight, water 3? Ratio 80
90
80
80
91
90
90
90
90
90
80
90

1: 2 1: 3 Is3 1: 3 1: 3 1: 3

1: 3 1: 3 1: 3 1: 3 3: 8 1: 3

Amount of to-

Kata- given _Λ

lysator catalyst

Rh + Os 0 , 15 + 0, 20th FeCl ₃ + Mn0 ₂ £> , 10 + ö, 05 NaOH 0 _r 04 Ru + NaOH 0 , 15 + Cf 04 MnO ₂ 0 , 30 •

Rh-KJs Rh-K) S Ru + Os Ru

0 _f 15 + σ, 14 0 _r 15 +0.14 0.15 +0.14 0.15

FeCl ₃ + MnO _A 0 _;

Table XVI (continued)

..- Bel- '
game Re-
active React
functional
> print ^ / argon
pressure 2) 1 Hour (psig) Amount of
added
water • to- oil-to-what-
ser weight
3) relationship Kata
lyser Amount of too
given / ν
catalyst • 111 1 288 (4100) 28.1 (400) 2) atü 80 1: 2 Rh + Os D _r 15 +0.20 112 1 297 (4225) 28.1 (400) 3) g 80 1: 2 Ru + 0s 0.15 +0; 20 cn
ο 113 1 288 (4100) 28.1 (400) 90 1: 3 FeCl ₃ + Mn ( ) ₂ 0.10 +0.05 CO
CO 114 1 302 (4300) 28.1 (400) 90 1: 3 Ru + Mn0 0.15 +0 _; 05 · ■ a> 115 1 302 (4300) 28.1 (400) 90 1: 3 Ru + Mn0 ₂ • 0.15 + 0.30 ο · 116 2 306 (4350) 28.1 (400) 80 1: 3 NaOH 0.04 O
in 117 1 299 (4250) 28.1 (400) 90 1: 3 MnO ₂ . 0.30 Remarks

4) The amount of catalyst added is given in g and in the
the same order as the corresponding catalysts listed *

Table XVII

gas 1'
Product composition Heaviness
end up Fixed
fabrics . percent - distance of ²⁾ H-C 3) API ⁴⁾
Spec. Weight Weight
Balance sheet at
game 8.6 Light "~~
■ ends 5.2 7.8 sulfur nickel Vanadium - - · 100.7 88 3.3 77.7 6.0 13.8 4'S - - - - 101 j 2 89 2.3 70.2 12.7 8.5 48 - - ■ - - 99.6 90 V 76.7 5; 7th 6.4 48 - - - - 97.2 91. 11.2 84.2 '8.6 5.0 56 - - 1.451 20.5 100.2 92 1.3 75 _r 2 27.1 l _T 0 63 95 74 1.362 20.5 99.4 93 12.1 70.6 8.3 7.7 36 69 77 1.441 22.7 100.8 94 0.3 72.0 16.8 35 97 84 1.513 - 99.7 95 2.7 75.2 21.1 h 3 52 - 86 1.408 20.8 99.7 96 • Si 71.6 23, .9 33 28 64 - 14.0 99.1 97 1; 7 68.3 28.9 3.3 25th •. 94 86 - - 99.8 98 66.4 - -

INJ CO

Table XVII . (Continued).

• Gas Product composition * ' Heaviness
end up Fixed
fabrics ,Percent distance of 2) H-C 3) ΑΡΪ ⁴ >
Spec. Weight • Jz 5 at
game S3 Easy
end up 32.3 . h ° sulfur 'Nickel Vanadium - 20.7 Weight -
Bilar 99 5.0 60.5 27.8 1.0 71 78 74 - - ICl, 2 W
ο
co 100 2.7 66.0 23.0 2.2 33 19th 70 - - 100.4 I. co
cn 101 8.0 72.1 14.7 8.5 ' 74 85 82 ■ - m 99.7 O
Cs 102 7.7 68.9. 22.4 ^X ' ³ 77 89 84 100.6 I. O 103 · 1.0 68.6 39.4 0.1. 80 '80 96 - 99 _T 8 cn 104 5.9 62.9 20.0 6.9 39 42 75 1.418 12.5 99.9 105 16.0 67.2 12 _T 0 • 9.0 4-9 77 96 1,442 18.9 99.7 106 .3.6 63.0 31.7 3.2 42 88 83 1.481 12.5! 100.9 107 1.0 54.9 25.0 V 37 82 88 1.435 12.1 100.2 108 ■ 3.1
8 _r l 67.8 26.8
30.0
* * 5.9 59 79 92 IW
mm 12.2
10.0 99.6 25223 109
110 62.0
61> 7 • 81
28 8th
98 88
76 99.3
100 ₇ 3

at
game Gas Product composition ' Heaviness
end up Fixed
fabrics Tabel XVII fFnr + -RA4-i7.i, nrtll 33 nickel 77 Vanadium 111 5.0 Easy
end up 43.1 3.4 2)
, Percent distance from 81
82 - 17th
■; 94 - • 112 V 48.5 35.2 5.1 sulfur 82 93 77 113
114 5.5
6.7 55.0 41.8
31.5 0.7
5.4 ·. - ■ 37 91. 91
95 115 5.7 52.0
56.4 32.4 2.7 80 - 86 91 S09 116 5.0 59.2 32.2 2.9 92 OO
cn 117 · 59.9 33.2 1.3 93 ο
"» Ν 5.7 59.8
Remarks ) 7 0 5

. . APt ⁴⁾ wt

Η-ά 3) specific weight balance "

.14.4 100.1

. «,« 100.0

99.9 i. - 100.0

1)% by weight based on the hydrocarbon feed material!

2) These values are obtained from analyzes of the combined light and heavy Ends preserved. ·,. ·

3) atomic ratio of hydrogen to carbon.

4) ⁰ API '' ■ ■ '

5) Total weight based on hydrocarbon and water feeds. materials and the catalyst, obtained as product and water. fc>

Table XVIII

Presence of a reactive oil-to-water additive from the outside. " Loose weight catalytic converter time ratio

93 no 1
* 1: 3 · ' ttt 92 no 3 . .1: 3 .098 50 94
99 Yes
Yes >
3
1 1: 3
1: 2 O 104 no. "1. 1: 3 70S 105
107 no
Yes 3 ·
1 . 1: 3
1: 3 106 Yes 3 1: 3 Remarks 1 Hour 2) mole% des Gas product

composition
of the gas product co ₂ CH ₍ Weight% H ₂ ■ 3.1 H of the gas
product. 2.8 5.2 6 » 1.3 3.3 5.2 8th, 11.2 - 4.5 5, 12.1 5.1 3.8 8th, 4.3 1.0 5.6 7, 1.0 3.0 3.0 s; g 3.7 7.1 ⁸ ; 3.6 4.5 , 16.0 i 4th 9 1 8th 4th 5 2 4th

K) I K> • OJ

In all cases the main component of the gas products is argon, which was used to pressurize the reactor and which is not listed in Table XVIII. · One change the oil-to-water weight ratio of 1: 3 to 1: 2 and / or increasing the reaction time results in increased yields of gas. The addition of a catalyst also gives an increase in the yield of gaseous products.

The presence of carbon dioxide and hydrogen among the gas products obtained in Examples 92, 93, 104 and 105 shows that hydrogen and carbon monoxide are formed even without the addition of external catalysts Swells, presumably because metals inherent in tar sand oils act as catalysts.

A comparison of the results shown in Table XVII shows that the addition of catalysts is generally a allows for a greater degree of desulphurization than is possible achieved when no catalyst is added from an external source will. The addition of a transition metal oxide or a basic metal hydroxide or carbonate, either alone or as an activator in the presence of a water reforming catalyst, greatly improves the level of desulfurization. However, with hydrocarbon feedstocks, excluding tar sand oils, the extent of desulfurization with increasing response time. In all cases the sulfur, which is removed from the oil as elemental sulfur and not in the form of sulfur dioxide or hydrogen sulfide obtain.

A comparison of the results listed in Table XVII shows substantial metal removal, even after one Reaction time less than 1 hour and even in the absence of an external source added catalyst. However, will by adding a catalyst and / or a transition metal oxide or a basic metal hydroxide or carbonate as an activator, the extent of demetallization v / pus improved.

509850/0705

Examples 118 to 171 relate to batch examples in a 300 ml Hastelloy alloy — C-Magne— Drive reactor using Khafji and C atmospheres— Residual oils. The properties of these residual oils are given in Table X indicated and marked with the letter "B". Examples 118-135 relate to Khafji atmospheric residual oils, whereas Examples 136-171 relate to atmospheric C residual oil. The reaction conditions used in these examples conditions are given in Table XIX. Unless otherwise stated in Table XIX, all experiments were carried out at 400.degree (752 P) carried out. The test results are in the table XX specified.

609850/0705

Table XIX.

O
CO
GXJ

Re-. React

At- action-

. _n ons -ι ) rinirlf 2)

season ¹ 'arucjc'

113 13 ^y '253 (360O)

119 8 ⁹ 256.5 (3650)

9.

120 2 320 (4550)

121 6 ⁹ 253 (3600)

122 ■ 6 ⁹ 253 (3600)

123 6 ⁹ 176 (2500)

124 6 313 (4450)

125 4 316 (4500)

126 1 309 (4400)

127 1 302 (4300)

128 1 292 (4150)

129 · 1 · 292 (4150)

130 1 '292 (4150)

ArgondrucJc

28.1 (400)

28.1. (400)

31.6 (450)

31.6 (450)

31.6 (450)

31.6 (450)

31.6 (450).

31.6 (450)

28.1 (400)

28.1 (400)

28.1 (400)

28.1 (400)

28.1 (400)

oil-to-water amount of weight added ratio of water 3)

1: 3.2

1: 3 _; 2

96

96

90

90

90

30th

90

90

90

90

90

80

90

Amount of catalyst added to catalyst

Os Ru ⁵ Rh ⁶ , Os

0.2

0.12

0 _→ 12, 0 _; 17th

Rh, Os ° r 15, 0.14 # Rh, Os 15, 0 _; 14th Ru, Os 15, 0.14 Ru, Os °, 3, 0 _f 4 FeCl ₃ , MnO ₂ 1, 0.05 FeCl ₃ , MnO ₂ °; 1, 0.05 he:
K> ^15. » 0.09
!

Table XIX (continued)

Egg React
functional
■ 7 / = i 4-1) Reak
functional
pressure 2) Argon- ₀ .
pressure ^Δ) Oil ~ to-water-
Weight reduction
ratio Amount of
added
Water ³ ^ Kata
lyser ■ amount of too
given QV
catalyst 0.2, 0.09 • « 131 Zi CX L. '
1 302 (4300) 28.1 (400) 1: 3 90 Ru, Os,
Cr ₂ O ₃ 0.15, 0 _r 2 132 1 288 (4100) 28.1 (400) ' 1: 2 80 Ru, Os 0.15, 0.2 - 133 1 281 (4000) 2 8.1 (400) 1: 1 60 Ru, Os . 0.15, 0.2 cn 134 1 299 (4250) 28.1 (400) 1: 2 80 Ru, Os 0.15, 0.2 ο
co 135 1 292 (4150) 28.1 (400) 1: 1 60 Ru, Os 0.15, 0.6 25223 cn 136 1 302 (4300) 2 8.1 (400) 1: 3 90 Ru, MnO ₂ 0.15, 10 O
"Ν,
O 137 2 302 (4300) • ■ 28.1 (400) 1: 3.75 80 Ru, NaOH 0.15, 0.2. 0.09 * 4
O 138 1 299 (4250) 28.1 (400) 1: 3 90 Ru, Os,
Cr ₂ 03 0.15, 0 _; 2 139 1 297 (4225) 28.1 (400) 1: 3 90th Rh, Os 0.15, 0.2 140 1 295 (4200) ' 28.1 (400) 1: 3 90 Rh, Os 0.15, 0.2 141 1 299 (4250) 28.1 (400) . 1: 3. 90 Rh, Os 0.15, . ° r ² 142 1 288 (4100) 28.1 (400) 1: 1 ' 60 Ru, Os 0.15, , 0.2, 0.3
i 143 1 323 (4600). 28.1 (400) ¹ 1: 2 80 Ru, Os,
H ₂ WO ₄ 0.15 _:

• Table XIX (continued)

cn ο to co cn O

at
game React
functional Reak
functional
pressure 2) Argon-p.
pressure ' 144 1 309 (4400) 28.1 (400) 145 1 313 (4450) 28.1 (400) 146 1 320 (4550) 28.1 (400) 147 2 295 (4200) 28.1 (400) 148 2 309 (4400) 2 8.1 (400) 149 2 309 (4400) 28.1 (400) 150 18 ¹¹ 274 (3900) 35.2 (500) 151 16 ¹² 265 (3775) • 31.6 (450) 152 16 ¹² 257 (3650) 35.2 (500) 153 6 ¹² 260 (3700) 154 2 320 (4550) 31.6 (450) 155 6 ¹² 183 (2600). ' 31.6 (450) 156 6 ¹² 253 (3600) 31.6 (450) 157 '6 320 (4550) 31.6 (450)

Oil-to-water weight ratio

Amount of added " water 3)

80

90 90 90 90

_9O 1O 90 96 96 96 90 30 90 90

Catalyst

Ru, Os, TiOo

KOH KOH Ru,

Ru, TaCl ₅ ,

■ Amount of 8) catalyst added

0.15, 0.2, 0.3

0.15, 0.3

Well ₂ CO ₃ O, 15, o _? 2, 0.3 Ru, Na ₂ CO ₃ 15, °; 3 I. Ru O, 12th 00 Os 0, 2 I. Ru O, 2 Rh, Os ο ·. 12, 0, 22nd Rh, Os 0, 12, Of 17th

Rh, Os

0.15, 0.14 NJ CO

Reac- reac-

Bex-
SDi el functional
time ^ functional
pressure 2) Argon--,
print ^ά ' 158 4th 313 (4450) 31.6 (450) 159 2 302 (4300) 28.1 (400) 160 1 300.5 (4275) 28.1 (400) 161 0.5 313 (4450) 28.1 (400) cn 162 0.5 308 (4375) 28.1 (400) 9 8 5 0 / 163
164 1
2 309 (4400)
309 (4400) 28.1 (400)
28.1 (400) CD
• <l
O
in 165
166 1
1 309 (4400)
295 (4200) 28.1 (400)
28.1 (400) 167 1 295 (4200) 28.1 (400) 168 1 302 (4300) 28.1 (400) 169 1 292 (4150) 28.1 (400) 170 1 295 (4200) 28.1 (400) 171 2 299 (4250) 21.1 (300)

Table XIX (continued)

Oil-to-water weight s ratio

1: 3 1: 2 1: 2 1: 3 1: 3 1: 3 1: 3 1: 3 1: 3

Amount of
added "
Water 3),. Kata-. -
lyser • • amount of too
given »
Catalyst ⁰ '' I. ro
cn
hv ^ 91 Rh, Os 0.15, 0.14 Ki
CO 80 Rh, Os 0.15, 0.14 —A
CO 80 Rh, Os 0.15, 0.14 90 Rh, Os 0.15-, 0.14 90 Ru, Os 0.15, 0.14. - Ru, Os 0.3, 0.4 Ru, Os 0.3, 0.4 ' - Ru, Os 0.3, 0.4? FeCl ₃ ,
MnO ₂ 0.1, 0.05 80 FeCl ₃ ,
. MnO ₂ 0.1, 6.05 90
90
90 . Ru, Cr ₂ O ₃
Ru, MnO ₂
■ Ru, MnO ₂ 0.15, 0.09
0.15, 0.05
0.15, 0.3 90 Ru, Ir ⁷ 0.10, 0.10

Table XZX (continued) Comments

1 Hour

2) atü (psig)

3) g

4) Added as OsCl ₃ ^# 3H ₂ O

5) Added as RuCl ₃ * 1-3H ₂ O

cn 6) Added as RhCl ₃ * 3HpO

2 7) Admitted as

⁰⁰ 8) The amounts of catalysts added are given in g

ο and in the same order as the corresponding ones

Q catalysts were listed. .

^ 9) The reaction temperature is 3 8O ⁰ C (716 ⁰ P).

^ 10) The water also contains 5 g of hexene as an additional source of hydrogen,

11) The reaction temperature is 370 ° C (698 ° F).

12) The reaction temperature is 377 ⁰ C (710 ⁰ F),

N. · CO

At- .
game composition Easy
end up Tabel Fixed
fabrics XX ¹ 50 Distance from 2) 84 Mass
Balance ³³ I. 118 gas 1.7 of the product ^ ' 6.2 percent 69 Vanadium nickel 98 99.3 00
I " 119 9.9 0 Heaviness
.End up 9.3 sulfur 82 - 98 99.6 120
121 9.6 57.3
88 _y £ 82.2 0.7
0 37 72 - 98 98.4
92.7 122 5.0
3.9 49.2 83.2 1.8 38 78 98 102.3 5 0 9 8 5 .123
124 4.0 37.4
69.9 37.0
j2 0.3,
9.8 ' 14th - 97.1.
103.6 ο 125 ² ' ⁵ 66.2 45.0 11.7 35 - - 98.3 cn 0 7 0 p. 126 ⁴ 6.8 60.7 60.8
13.2 4.8 . 22nd
22nd . - 101.2 223 127 ⁵ . ² r ° 58.2 15.3 10.8 101.9 128 0 56.6 38.3 2.0 100.4 129 0 57.2 32.0 ¹ T ³ 100.5 130 0 42.7 43.5 2.7 100.0 7.3 43.4 47.1

Table XX. (Continuation)

At- .
■ game Composition Easy.
end up of the product ^ ' Fixed
fabrics percent Removal of - 76 2) • Mass
Balance ³ ' CO
N) NJ)
cn
NJ 131 gas 51.6 Heaviness
.End up 4 _T 2 sulfur Vanadium 76
92 nickel 100.1 I. CO ■ .132 6.7 47.0 37.5 2.6 61 80 92 26th 99.2 ' CO 133
134 2.4 52.6
52.2 48.0 2.6
2.3 72 98 92. 52 . 98.9
99.7 cn
CD
00 135 1.5
4.5 45.5 44.0
41.1 2.5 26th 98 . 81 99.3 ό 136 2.2 54.9 50.0 3.5 13th 84 "74 99.5 - «4 137 4.0 66 _r 8 37.6 6.1 72 72 75 100.4 ö
Oi 138 3.3 57.3 29.8 27 92 88 " 100.5 139 6.7 58.9 35.3 ' 2.2 24 76 81 101.1 140 7.0 50.5 39.1. 3.4 - - 99.3 141
142 2.9 56.9
53.1 43.2 M. 77 - 100.2
99.8 143 3.3
2.8 68.3 38.1
42.3 3.4 23
23 62
38 99.6 144 2.0 61.3. 26.4 3.9 - 56 100.4 3.3 · 31.8 - 88 ■

Table XX (continued)

composition Easy.
end up of the product ^{x /} Fixed
fabrics percent Removal of 2). . . . ' · ■ · ' ) At- .
game gas 54.3 Heaviness
. end up 7.5 sulfur Vanadium. nickel ,. Mass
Balance ³ 145 51.7 ■ 36th, 9th 6.7 79 92 100.6 146 . 2.0 48.0 39.7 9.5 82 90 101 ·, 1 147 V 62.0 43.3 - - 102.7 • 148 3.6 60 _r 6 31.2 ■ V - '100j4 149 4.3 36.6 30.2 6.1 "- 98.0 150 6.3 17.0 48.0 ^- 10 _D 2 47 - ■. ■ - 96.6 151 22.0 8.0 60.0 10.0 42 - ■ r 91.5 152 12.0 56.8 71.1 5.3 30th 9I ₇ 8 153 66.8. 38.6 4th 30th • 101 _; 3 154 6.3 35.3 26 _r 7 0.7 '/ 23 103.8 155 • .2.5 53.0
70 _; 5 62.1 1.3
10, 30th ■. ·. ~ 98.4 2522 156
157 V
4.3 38.0
14.6 32
92. 100.7
99.7 1 ^ V
CO

• At- . composition Easy
end up of the product * ' Fixed
fabrics present Removal of 2) Balance ^3Y I. 158 gas 58.5 ■ Heaviness
.End up 7.2 sulfur Vanadium nickel 100.0 03
I. 159 6.3 67.8 21.0 7.4 51 100 _r 2 160 4.4 55.0 25.0 1.9 22nd 92 100 _; 2 161 2.0 54.7 43.3 2.3 26th 84 102 j 5 cn
ο '162 2.0 61.7 4o; s ·. 1.2 67, 92 '- 101.3 CO
OO
cn 163 0.7 61.8 41.3 2.4 80 56 '_'_> - 99 _r 9 O . 164
165 ⁶ 1.7 70.5
64.0 33.5 3.9,
V 66 92 100.0
100.3 Ö 166 2.2
0.3 53.4 25.7
33.3 0.6. . 24
- 68 80 - ''
98 99 _f 9 167 0 54.9 49.5 IfS , 77 • 98 - 99.9 '' 168 0.7 45.3 42.8 ^! 2.5 '. ' 65 98 101.1 ■ 169 9.1 47.5 44.6 l _r 9 '' "79 98 101.1 170 6.0 56.0 44.6 2.7 . , 80 98 99.9 »" Ο
cn 171 0.3 56.0 41.0 6 _; 0 . 79 98 - 100.2 NJ 7.0 31.0 mm 9m * mm

Table XX (continued)

Remarks

1)% by weight based on the hydrocarbon feed.

2) These fourths are obtained from analyzes of the combined light and heavy ends.

3) Total weight percent of hydrocarbon and water feed

cn and catalyst, obtained as product and water.

to 4) The combined fractions of light ends and heavy ends

co.

cn had an H / C atomic ratio of 1.524.

σ '

* "· - 5) The combined fractions of light ends and heavy ends cn

Θ . .σι

^ j had an H / C atomic ratio of 1.644. ,

o ° i 6) The combined fractions of light ends and heavy ends

had an atomic ratio of 1.7.

K) N) CO

The results in Table XX indicate that cracking and desulfurization occurred in tests performed in the absence a catalyst added from an external source can be carried out, as well as in experiments in which a catalyst is added. However, the addition of a catalyst from an external source increases the yields of gases and light ends strong, even after a very shortened reaction time. The addition of an activator to the catalyst system causes an increase in both the absolute yield of the gases and in the ratio of the yields of gas to solids. The use of enough water to give a water density of at least 0.1 g per ml i.e. the Use of a hydrocarbon feedstock and water in proportions such that the weight ratio of Water-to-hydrocarbon feed relatively high istj causes a greater yield of gases and light Ends and a greater desulfurization than when the weight ratio of water-to-hydrocarbon is relatively low. The addition of 1-hexane as a hydrogen donor to the reactor Mixture gives a lower yield of solid product and an increased yield of light ends.

In general, the amount of desulfurization increases when the reaction temperature is higher when the reaction time is in a certain range when the water-to-hydrocarbon f-feed weight ratio is higher and when an activator is added to the catalyst system. The use of activators, even in the absence of a catalyst, gives satisfactory desulfurization.

The sulfur that is removed from the residual oils appears in the products as elemental sulfur when the density is at least 0.1 g per ml, i.e. if a relatively low hydrocarbon-to-water feed weight Ratios such as 1: 1, 1: 2 and 1: 3 are used. When the water density is less than 0.1 g per ml, i.e. when a relatively high hydrocarbon-to-water weight ratio, like -1: J, is used, a part of the

5 0 9 8 5 0/0705

hydrogen feed removed sulfur in the products as hydrogen sulfide.

In general, the extent of EntnetallisieriaTMi increases when the water-to-hydrocarbon feedstock is Lal - Weight ratio is slightly higher "when using an activator Catalyst system is added and when the reaction time lies in a certain range. The use of an activator satisfactory demetallization results even in the absence of a catalyst.

Examples 172 to 188 relate to batch experiments in a 300 ml Hastelloy-Alloy C Magne-Drive autoclave using C vacuum residue and atmospheric Cyrus residue oil. The characteristics of this; Residual oils are given in Table X and ^denoted by the letter ® "B tT. Examples 172 to 174 relate to C -" ^ akuusm-Restol "whereas Examples 175 to 188 relate to atmospheric Cyras - residual oil. The reaction conditions used in these examples are given in Table XXI. All tests are performed at 400 ° C (752 ° F). The experimental conditions are given in Table XXII.

509850 / Ö7ÖS

Example

172
173
174
175
176
177
178

179
180
181
182
183
184
185
186

. 187

188 '

Reaction reaction
time ^) pressure 2)

1
2
1
2
2
2
2

2
2
4th
2

. 2
2
1
1

1
1

299 (4250)
299 (4250)
292 (4150)
320 (4550)

309 (4400)
312 (4450)
302 (4300)

288 (4100)
250 (3550)
309 (4400)
306 (4350)
306 (4350)
299 (4250)
306 (4350) '
309 (4400)

295 (4200) '
295 (4150)

Argon-ρ » pressure '

400 (28.1) 400 (28.1) 400 (28.1) 450 (31.6) 450 (31.6) 450 (31.6) 400 (28.1)

2 400 (8.1) 400 (28.1) 400 (28.1) 400 (28.1) 350 (24.6) 400 (28.1) 28.1 (400) 28.1 (400)

28.1 (400). 28.1 (400)

Table XXX

Oil-to-water, weight ratio

1: 3

1: 3

1: 3

1: 3 '.

1: 3

1: 3

1: 2.3

1: 2.3

. . ·. 1: 2.3 .. 1: 2.3 1: 2.3 1: 2.3 1: 3 1: 3 1: 3

1: 3 1: 2

Amount of
added '
Water ³ ' Catalysis,
. sator mm • amount of too
given 7)
Catalyst ■ 0.12 90 RuW, Cr ₂ C Rh ⁶ + 0s »3e, 13, Py2. ^ 09 '90 Ru, Os, Cr ₂ O ₃ Rh, Os
Rh, Os 0 _r 15, (J, 2, ö _; 09 0.15.0 _r 14 90 KOH 1 Or 15,0,14
r
CO 92 Ru '90 91 70S
70 ⁸

71 ^C

70 ^ξ

9Q

90 80

10 11

Ru

Ru

Ru

Ru + Os

Ru + Os

Ru Η «Os

FeCl ₃ + FeCl ₃ +

0.12

0.12 0.12 ί, 12, 0.14

0,12,0,14

MnO ₂ MnO ₂

0,1,0.05 ι /

0,1,0 / 05 ^

Table XXI (continued) Comments

1 Hour

2) atü (psig)

3) g

4) Added as RuCl ₃ * 1-3 H ₃ O '

2 5) Added as OsCl ₃ OH ₃ O

Q ₀ δ) Added as RhCl ₃ O HpO

ο 7) The amount of catalyst added is expressed in g and in '

CS listed in the same order as the corresponding Kata- \ o

Q lysers are indicated. '

cn ..

8) The water also contained 10 g of ethanol.

9) The water also contained 10 g of 1-hexene.

10) The water also contained 20 g of ethanol.

11) The water also contained 30 g of ethanol.

ISO K) CO

Table XXII

at
game Composition of the product ^iy Easy
end up , Heaviness
. end up • 24.3 pest
fabrics percent ■ - Distance of 2) Mass.
Balance ^3Y ■ 100.5 1
VD
O
I. • 172 gas 32.3 58.0 79.0 3.0 sulfur - ,Nickel Vanadium 100 _; 6th 101.6. 173 6.7 34.0 47.6 42.0 5.3 84.7 - 92.6 20.5 100.5 99 _f 2 174 13.1 29.7 60.8 35.2 - 8.2 56.7 - 66.7 76.5 100.1 99.8 cn
ο 175 1.3 55.6 27.3 41.6 10.0 90.0 53.0 96 _r 0 24.0 100.7 ' CD 176
177
178.
179 49.9
6.4 33.0
83.9
33.3
44.5 33.7 12.0
9.3
11.8
28.3 36.2 68.0 - - 100.6
• 99.8 cn
O
O
O
cn 180 4.6
7.0 - 44.1 6.3 26.9
21.3 76.0 - - - TsJ 181 - 66.6 75.5 13.4 80.2 - ■ - cn
K) 182 - - 6.7 - - ■ - K)
CO 183 - - 5.7 - - - t . · ■ » . 184 - 55.0 10.0 - - 185 - 53.5 7.7 - - 186 ¹ I ⁷ 64 ^ 2 5.7 96.0 24.0 187 0.3 47.6 2.7 87.4 0 188 3.6 23.0 1.8 99.0 0 0 95.0 17.0

Table XXII (continued)

Remarks.

ot 1)% by weight based on the hydrocarbon feed.
ο

co 2) This fourth is made up of analyzes of the combined light and heavy

_o Ends preserved. ^ ₀

ο 3)% by weight, based on the hydrocarbon and water supply!

_o cing material and the catalyst, obtained from the product and water.

NJ CaJ

The results in Table XXI show that satisfactory desulfurization and demetallization of C vacuum and atmospheric residual Cyrus oils. The split of the C vacuum residual oil results in some formation of Gases and light ends, but not to the extent that tar sand oils and khafji and C-atmosphere residual oils do notices.

Cleavage of the Cyrus atmospheric residual oil occurs more easily than the cleavage of the C vacuum residual oil, but the Cyrus atmospheric residual oil appears to be more refractory than the khafji or C-atmosphere residual oils. The splitting of the residual Cyrus atmospheric oil in the absence of a catalyst added from an external source gives a large yield of solids Products. The cracking of this hydrocarbon feed in the presence of a ruthenium catalyst or a rhodium-osmium mixed catalyst from an external source are added indicates an increase in the yield light ends, but the yield of solid products is not lowered. However, cracking results in this hydrocarbon feed in the presence of an iron-manganese or ruthenium-osmium mixed catalyst or with a hydrogen donor, such as ethanol or 1-hexene added to the water solvent, a lower yield of solid products and an increased yield of light ends.

Example 189 explains the denitrification of hydrocarbons by the process according to the invention. A 2-hour batch is carried out in a 300 ml Hastelloy alloy B Magne-Dash autoclave. In this example, 15.7 g of 1-hexene with 91.4 g of water, which contains 1 ml (0.97 g) of Parrol, in the presence of 0.1 g of soluble RuCl ₃ · 1-3H ₂ O catalyst at a Reaction temperature of 350 ° C (662 ° F) and a reaction pressure of 237 atmospheres (3380 psig) and argon pressure of 45.7 atmospheres (650 psig). The products include gases in an amount of 10.1 liters at normal temperature and pressure and 14.3 g of liquid hydrocarbon product. The gas products mainly consist of argon

609850/0705

and contain 6.56% by weight of carbon dioxide and 1.13% by weight Methane. The amount of hexane in the product is 46.6% by weight based on the 1-hexane feed. The liquid one Hydrocarbon product contains 888 ppm nitrogen at one 93% removal of nitrogen from the hydrocarbon feed.

Examples 190 to 192 illustrate that the catalyst of the process according to the invention is resistant to nitrogen. she concern 4-hour approaches in a 300 ml Hastelloy alloy B Magne-Dash autoclaves. In each of these examples, 12.8 g of 1-hexene are mixed with 90 g of water at one reaction temperature of 350 ° C (662 ° F) under an argon pressure of 45.7 atmospheres (650 psig) and in the presence of 2.0 grams of silica, which Contains 5% by weight ruthenium catalyst, implemented. The supported catalyst was in oxygen for 4 hours Calcined at 550 ° C. Examples 190, 191 and 192 are run at reaction pressures of 246, 246 and 239 atmospheres (3500, 35.00 and 3400 psig). The reaction mixture in Examples 191 and 192 additionally contains 1 ml (0.97 g) of pyrrole. Example 192 is carried out under conditions identical to those used in Example 191. Additionally was the same catalyst as used in example 191 is reused in example 192. The yields of hexane Examples 190, 191 and 192 are 16.6, 14.0 and 13.9 weight percent, respectively, based on the 1-hexene feedstock. Within the usual experimental margins of error, these yields indicate that there is no nitrogen poisoning occurs.

Examples 193-202

Examples 193-202 relate to semi-continuous 400 ° C (752 ° F) flow method of undistilled tar sand oils under a variety of conditions. That The flow system used in these examples is shown in FIG. In order to start the experiment, inert 0.3-2 cm (1/8 inch) diameter balls made of refractory Alumina or irregularly shaped pieces of titanium oxide

509850/0705

with 2% by weight ruthenium catalyst deposited thereon, through the top 19 into a 5.5 cm (21.5 inch) long Värtikal Hastelloy alloy C-tube reactor 16 having an outside diameter of 2.5 cm (1 "inch) and an inside diameter 0.25 inch (0.63 cm). The lid 19 is then closed, and a burner (not shown is) is given by the length of the tubular reactor 16. The tubular reactor 16 has an effective total heated volume of about 12 ml, and the packing material has a total effective heated volume of about 6 ml approximately 6 ml of effective heated free space in tubular reactor 16.

All valves except 53 and 61 are opened and the flow system is purged with argon or nitrogen. Then, with valves 4, 5, 29, 37, 46, 53, 61 and closed and Annin valve 82 set so that it releases gas from the flow system when the desired pressure in the system is exceeded, the flow system pressures in the range of about 70.3 atmospheres (1000 psig) to about 141 atmospheres (2000 psig) by argon or nitrogen is allowed to enter the system through valve 80 and line 79 ;. The valve 80 is then closed. Then the pressure of the flow system is brought to the desired reaction pressure by the Valve 53 opens and pumps water through the Haskel pump 50 and the line 51 into the water tank 54. The water serves to further compress the gas in the flow system, thereby increasing the pressure in the system. If a bigger one Volume of water than the volume of water in the tank 51 is required to bring the pressure of the flow system to the desired level To increase the value, valve 61 is opened and additional water is added via line 60 to the storage tank pumped. When the pressure of the flow system reaches the desired pressure, valves 53 and 61 are closed.

509850/0705

A Ruska pump 1 is used to remove the hydrocarbon fraction and pump the water into the tubular reactor. The Ruska-Purape 1 contains two 250 ml drums (not shown are), with the hydrocarbon fraction in one drum and water in the other drum at ambient temperature and atmospheric pressure. Pressure pistons (not shown) inside these drums are rotated manually until ' the pressure in each drum is the pressure of the flow system is equivalent to. When the pressure in the drums and in the flow system are the same, the control valves 4 and 5 become opened to allow the hydrocarbon fraction and water from the drums to flow through lines 2 and 3. At the same time, valve 72 is closed to allow flow in line 70 between locations 12 and 78 to avoid. The hydrocarbon fraction and water streams are then at point 10 at ambient temperature and at the desired pressure they combine and flow through line 11 and enter the bottom 17 of the tubular reactor 16 a. The reaction mixture flows through the tubular reactor 16 and leaves the tubular reactor 16 through the side arm 24 at the point 20 in the wall of the tubular reactor 16. Die Location 20 is 19 inches from floor 17.

When the solution flows through tubular reactor 16, one begins to heat the tubular reactor 16 with the burner. During the heating of the tubular reactor 16 until steady state conditions are reached, the valves 26 and 34 are closed and the valve 43 is opened so that the mixture can flow in the side arm 24 through the conduit 42 and enter the storage tank 44 and be stored there can. After steady state conditions are reached, valve 43 is closed and valve 34 is closed during the desired time opened so that the mixture in the side arm 24 flow through the line 33 and into the Enter product receptacle 3 5 and can be stored therein. After the product in the product receiving vessel 35 while the desired time has been collected, valve 34 is closed and valve 26 is opened so that the

5098S0 / 0705

Mixture in the side arm 24 can flow via the line 25, enter the product receptacle 27 and there during can be stored for a further time. Then the valve 26 is closed.

The material in the side arm 24 is a mixture of gaseous and liquid phases. When such mixtures are in the storage tank 44, product receptacle 35, or product receptacle 2 7 enter, the gaseous and liquid phases separate, and the gases exit the storage tank 44, the product receiving vessel 35 and the product receiving vessel 27 üher the lines 47, 38 and 30 and are transferred via the line 70 and the Annin valve 82 into a storage vessel (the not shown).

If more than two batches of product are collected, valve 29 and / or valve 37 is opened to allow product from the product receptacle 27 and / or 35 and to enable the same product receptacle and / or product receptacles can be used or can to collect additional approaches of the product.

Towards the end of an experiment - after the desired number of product batches has been collected - the temperature becomes of the tubular reactor 16 is lowered to ambient temperature, and the flow system is relaxed by opening the valve 84 opens in line 85 and blows off into the atmosphere.

The diaphragm 76 measures the pressure differential along its length of the tubular reactor 16. No solution flows through the line 74.

The API specific gravity of the collected liquid products is measured and their nickel, vanadium and iron contents are determined by X-ray fluorescence.

S098SG / 0705

The properties of the tar sand oil feed materials not yet distilled, which were used in Examples 193-202 are given in Table X "The tar sand" oil feed contained 300 to 500 ppm iron, and the 300 ppm level was used to determine the percentage of iron removed in the product. The search conditions and the properties of the products formed in these examples are listed in Table XXIII. The liquid hourly space velocity or the liquid hourly space velocity (LHSV) was calculated, by calculating the total volumetric flow rate in ml per hour of water and oil feed material, flowing through tubular reactor 16, through the volumetric free space in tubular reactor 16, i. 6 ml, divides.

509850/0705

Table XXIII

- «a cn

Reaction pressure 1)

LHSV

2)

Example 193

288 (4100)

1.0 1: 3

01-to-water servo lumetric flow rate ratio refractory packing material sterling sound

Number of products collected during this time 3)

Example 194

284 (4040) '

1: 3

Ru, Ti

Ex, 195

285 (4060)

1.0 1: 3 For sp.
196

287
(4080)

At sp,
197

288
(4100)

2 _y 0
• 1: 2

At sp, 198

288 (4100)

2.0 1: 2

Ex. 199

288 (4100)

2.0 1: 3

Product features
API-spec. 21.0
.Weight 4) 95 21.0 23.0 20.0 % distant
nickel 97 77 84 69 % distant
Vanadium 98 81 96 ' 99 % distant
iron 99 98 92

17.8

97

59

17.3

69

54

21.0

64

73

99

Example 200

2 (4100) 2.0 1: 3

fireproof fireproof solid solid solid Ru, Ti 'Ru, Ti tone tone · tone - tone

1 +

Ex. Ex. 201 ■

283 (4020) (4040) 2.0

1: 3

Ru, Ti Ru-, .Ti

22.9 20.0 * 98 20.0 • 69 69 93 cn NJ 59 60, '77 NJ CO ^ 99 .98 CO

Table XXIII (continued)

Remarks

1) atü (psig)

2) hours ~ ¹
en

ο 3) The numbers show the 7 to 8 hour period after the start,

co during the feed material through the tubular reactor 16

Q flows. ''

O 4) ° API '*

ro er «fsj ho

The flow method used in Examples 193-202 can also be modified to produce a slurry of oil shale solids, tar sand solids or coal solids in a fluid containing water Pumps material through the tubular reactor 16. In this case, the refractory alumina balls would be in that Tubular reactor 16 does not exist, and storage tank 44 and product receptacles 27 and 35 could be equipped with a Apparatus, for example a sieve, may be equipped to remove the spent solids from the recovered hydrocarbon product to separate. Alternatively, tubular reactor 16 can be filled with oil shale, tar sand, or coal solids be packed instead of or in addition to the packing materials used in Examples 193 to 202. This continuous and semi-continuous flow treatment can be used in the recovery process itself.

Examples 203-226

Examples 203-226 use coal feedstocks processed to some extent in a variety of conditions. These examples illustrate that liquids and Gases are obtained and that the liquids obtained are split and desulfurized in the process according to the invention and that the remaining solid coal is desulfurized. Unless otherwise stated, the the following procedures are used. The coal feedstock, the water-containing fluid material, and the components of the catalyst system, if used, are poured into a 300 ml Hastelloy alloy-C at ambient temperature Magne-Drive autoclave, which is used in batches, is added, and the reaction mixture is added to the autoclave mixed. The components of the catalyst system are used as solvents in the water-containing fluid material or as solids in slurries from the water fluid material added. Unless otherwise stated, sufficient v / ater is added in each example, so that at the reaction temperature and at the pressure and the

S098S0 / 0705

reaction volume used, the density of the water is at least 0.1 g per ml.

The autoclave is flushed with an inert gas, namely argon, and then closed. This inert gas is also added to increase the pressure in the reaction system. The proportion of argon in the total pressure at ambient temperature is called argon pressure.

The temperature of the reaction system is then increased to the desired value, and the dense, fluid phase, which contains water, forms. It takes approximately 28 minutes to bring the autoclave from ambient temperature to 349 C (660 F) heat. It takes approximately 6 minutes to increase the temperature from 349 ° C (66O ° P) to 371 ° C (700 ° F). Approximately an additional 6 minutes are required to increase the temperature from 371 ° C (700 ° F) to 39.9 ° C (750 ° F). If the desired The final temperature is reached, the temperature is kept constant for the desired time. This constant End temperature "and the time at this temperature are defined as the reaction temperature and reaction time. During the reaction time, the pressure of the reaction system is increased as the reaction proceeds. The pressure at the beginning of the The reaction time is defined as the reaction pressure.

After the desired reaction time at the desired reaction temperature and the desired reaction pressure is the Phase from the dense, fluid material, which contains water, relaxed by being released from the reaction vessel by relaxation distilled off, whereby argon, gas products, water and "oil" are removed and "bitumen", a solid residue and catalyst, if present, remain in the reaction vessel. The "oil" is the liquid hydrocarbon fraction that is present at or boiling below the reaction temperature, and the "bitumen" is the liquid hydrocarbon fraction which is above the reaction temperature boils. The solid residue that remains is solid coal.

S09850 / 0705

The argon, the gas products, the water and the oil are stored in a pressure vessel that is cooled with liquid nitrogen, caught. The argon and the gas products are removed, by warming the pressure vessel to room temperature, and then the gas products are determined by mass spectroscopy, gas— Chromatography and infrared spectroscopy analyzed. The water and oil are then compressed from the pressure vessel with Gas flushed out, and occasionally heating the kettle. Then the water and oil are decanted by means of decanting separated. The oil is examined for sulfur content using X-ray fluorescence.

The bitumen, the solid residue and the catalyst, if any, are extracted from the reaction vessel with chloroform. washed out, and the bitumen dissolves in this solvent. The solid residue and the catalyst, if any, are then separated from the solution containing the bitumen by filtration. The bitumen and the solids are analyzed for their sulfur content, whereby the same procedure as used for oil analysis.

The weights of the various components of the added and isolated fractions are given either directly or indirectly determined by differences in the various stages during the procedure.

Three coal samples were used in this work. The samples are obtained in the form of chunks that have been ground and sieved to obtain fractions with different particle sizes. The particle size and the The moisture and sulfur contents of each sample used are given in Table XXIV. Samples A and B v / earth obtained from the Commonwealth Edison Company, while Sample C is an Illinois Mr. 6 seam coal produced by Hydrocarbon Research Incorporated. Sample A is a sub-bituminous coal, while Samples B and C are are highly volatile bituminous coals. These samples will be. ' kept under a blanket of argon until used.

6098S0 / 0705

For Examples 203-226, the liquids and gases are batch recovered from the coal samples listed in Table XXIV using the procedure described above. These experiments are carried out in a 30 ml Hastelloy alloy C Magne-Drive autoclave. The test conditions and the results obtained in these examples are given in Tables XXV and XXVI. give. RuCl ₃ '1-3HpO is the catalyst in Examples 203-224 and NaOH is the catalyst in Examples 225-226.'

In these examples the liquid hydrocarbon products either as oils or as bitumens, depending on whether such liquid products from the autoclave ■ ven can be distilled off when the autoclave is depressurized at the test temperature used can. Oils are such liquid products that can be distilled off by relaxation at the test temperature, whereas the bitumens are those liquid products that remain in the autoclave.

The weight balance shown in Table XXVI is obtained by adding the sum of the weights of the gaseous, liquid and solid products to be won and the weights of water, argon and catalyst, if used, which are obtained by the sum of the weights. Money, Water, co-solvent, argon and catalyst, if used, which were initially placed in the autoclave divides. The product composition is expressed as% by weight to be moisture-free And it is calculated by dividing the weight of the particular product in grams through the Difference between the weight of the coal feed in grams and its moisture content in grams. Of the Percentage of coal conversion is 100 minus the weight% of recovered solids.

6098S0 / 070S

The results of Table XXVI illustrate that essentially complete conversion of the carbon solids occurs
bituminous and sub-bituminous coal occurs when using the method of the invention. In all cases in which the sulfur content of the products has been determined,
there is also essentially complete desulfurization. The use of a catalyst in the process according to the invention in Examples 218 to 226 results in an increase in the formation of the oil fraction, based on the gas and bitumen fractions.

The results of Examples 211, 212 and 214 show that
the organic co-solvent does not contribute to the amount
on recovered solid product. The amount of solid product that remains after processing under the conditions of the process of the invention is a good measure of the extent to which solid coal is converted to gas and liquid
Products, even in the presence of a co-solvent. In general, the extent of coal conversion increases sharply,
when a saturated non-aromatic oil or biphenyl is used as a co-solvent. There were no attempts
carried out to distinguish between the proportion of the coal feed and that of the co-solvent in the yields
Distinguish gas and liquid products when a co-solvent is used.

S098S0 / 070S

Table XXIV

money
sample Λ)
Particle size Moisture
salary ² > sulfur
salary 3) A. 1.68-0.42 (10-40) 22.2 0.74 B. 2.00-0.42 (10-40) . 9.7 4.5 c ⁴⁾ > 0.177 (> 80) 2.7 .4.9

Remarks

1) mm (mesh)

2)% by weight

3)% by weight, on a moisture-free basis

4) pre-dried

S098S0 / 0705

Table XXV

May be-
sciel Coal
probel) ', Reaction p)
temperature Reacti
onszeit ^ Reaction
print ⁴ ' argon
pressure 4) 203 A. 400 (752) 3 295 (4200) 24.6 (350) cn 204 B. 400 (752) 3 299 (4250) 17.6 (250) 0985C 205
206 C.
C. 365 (689)
400 (75.2) CM CM 260 (3700)
313 (4450) 31.7 (450)
28.1 (400) ο 207 C. 399 (750) 2 302 (4300) 17.6 (250) 705 208
209 C.
C. 400 (752)
400 (752) 2
2 302 (4300) ■ 17.6 (250)
. 17.6 (250) 210 .. C. 400 (752) 2 320 (4550) 17.6 (250) 211 400 (752) 2 320 (4550) 17.6 (250) 212 - 400 (752) 2 302 (4300) 17.6 (250) 213 C. 400 (752) 2. 302 (4300). 17.6 (250) 214 400 (752) 2 · 302 (4300) (250)

Granted

Admitted Admitted Coal-to-Co- catalyst-water-solvent- weight ratio. Quantity ^ 'quantity

90

90 150

90

85 100

90

90

90

90

90

90:

0.56 - 0.56 - 0.33 - 0.56 - 0.59 ' 5 0.20 - 0.22 • 20th 0.22 40 0 40 0 40 • 0.22 20th 0 40

ρ · O cn

Table XXV (continued)

at
game Money-
probeD '. Response S-ρ ^
temperature Reacti
onszeit ^ Reaction
print ⁴ ' . argon
pressure 4) Granted _.
Amount of water ^ Coal-to-
Water-
Weight ratio * Admitted
Co- ··
Solver
Menqe ^ ' Added.
Catalysis
sator
quantity ^) r 215 .400 (752) ■ 2 292 (4150) 17.6 (250) 90 0 30 ¹⁰ 0.15 ·. * en 216 C. 400 (752) 2 295 (4200) 17.6 (250) 90 0.22 20 ¹⁰ - 0.15 ο
co 217 B. 400 (752) 2. 302 (4300) 1-7.6 (250) 90 0.22 20 ¹⁰ 0.15
0.15 00
cn
O 218 • A 400 (752) 3 304 (4325) 17.6 (250) -. 90 11.56 - ■, 0.15 ¹ ^ O 219 B. 400 (752) .3 299 (4250) ■ 17.6 (250) 90 0.56 - ■ O, 15 ¹³ 705 220 ¹¹
221 A.
C. 400 (752)
400 (752) 2
2 295 (4200)
309 (4400) ■ 17.6 (250)
17.6 (250) 88.7
90 0.56
0.56 O, 15 ¹³ 222. C. 400 (752) 2 292 (4150) 17.6 (250) 90 6.56 —_ 0.5 223 ' C. 400 (752) 2 285 (4050) 17.6 (250). 85 0 _T 59 N3
0.5 'O ₁ 224 C 400 (752) 2 302 (4300) 21.1 (300) 90 0.22 20 ⁸ 225 A. 400 (752) 2 295 (4200). ' 17.6 (250) 90 0.56 .- 226 C. 400 (752) 2. 295 (4200) " 17.6 (250) 90 0.56. ' . - '

Table XXV (continued)

Remarks

1) The samples correspond to the letters given in Table XXIV.

2) ° C ( ⁰ P)

3 hours

4) atü (psig)

5) g

6) Methyl alcohol is used as a co-solvent.

cn 7) Biphenyl is used as a co-solvent.

to 8) The co-solvent is a highly saturated solvent-extracted base oil,

oo which does not contain sulfur, 4.5% by weight of aromatic carbon atoms and

cn contains 33.7% by weight naphthenic carbon atoms and is API-specific

O has a weight of 32.1 ° and a density of 0.863 g per ml. '

O 9) The co-solvent is a highly saturated, hydro-refined white oil which is O

* 4 no sulfur, no aromatic carbon atoms and 44.3% by weight ^ro

Ό contains naphthenic carbon atoms and has an API-specific weight of ι ^m 28.2 ° and a density of 0.833 g per ml.

10) The co-solvent is decanted oil, an aromatic waste product that comes from the catalytic cleavage of cyclones is removed, and it contains 3.5 wt .-% Sulfur and 51% by weight of aromatic carbon atoms and is API-specific Weight of 1.8 °. ·

11) In addition, 1.2 g of 85 percent strength by weight phosphoric acid in water are added.

12) The catalyst system also contained 0.10 g of IrCl-, -1-3H-O as catalyst and 0.3 g sodium carbonate as an activator.

13) The catalyst system also contained 0.30 g of sodium carbonate as an activator.

Ca) Ca)

Table XXVI

Weight

1) 2) ^ Koh- 3)

Product Composition Product Composition Ie-Um- Sulfur Content

At- .. 4) .. a) wall weight

game gas 01 bitumen solid Sas 01 bitumen solid oil bitumen solid balance

cn ^{203 5} > ^{2 4} * ^{3 3} »6 · 26.3. 13 11 9.3 68 32 - - - 103.4

S ^{204 3} ' ^{2 4} ' ^{5 2} ' ^{6 34} T ³ ' .?, I 10 5.8 76 24. - - 24. 101.2,

»205 7.4 1.3 7.7 36.2 ' _t 4.5 · 2.7 ' 16

O 206 3.6 6.0 1.7 34.9 7.4 12. 3.5 72 28 .- - 2/8 105.1

O 207 6.9 5.4 0.6 37.0 - - - ₇₆ 24 - - - 100.9

O 208 I ₁ I 5.6 0.6 14.0 5.7 . 29 3.1 72 28 3.1 - 2.2 101.5

^6X1 209 - 19.1 1.1 13.6 - -

210-13.4 33.8 4.4 11.9 - - ·. - ₆₁ 39 - - 2.2. "98.9

211 ■ 1.4 36.8 2.4 0 - - - 0 0 - - - 102.4

212 3.3 13.2 20.4 0 - -._ 0 0-- - 101.4

213 3.3 18.9 3.9 12.1 · - - -. 62 38 - - 2.2

214 0.9 18.8 12.4 . 0 "- - '- V ₀ - - - 102.0

215 0.6 22 9 0.9 - - _< - ₀ 0 - - - 106.0

216 1.0 18.8 4.8 15.2 ^ - - '78 22 · · -. - - '99.5

217 2.3 41.6 4.0 15.6. - ·. - 86 14 -. · - -. lOl'o

68 32 76 24 74 26th 72 28 76 24 72 28 70 30th 61 39 0 0 0 0 62 38 0 0 0 0 78 22nd 86 14th

at
game Product composition oil Remarks
1 ·> rt Bitumen] Table XXVI <continued) , 2 15th
6.2 oil Weight -
% Koh- 3)
Ie-Um- sulfur content - 67
78 33
22 1.0 Bitumen 'JPe fabric I. ■ 218
219 gas 3.6
² ' ⁶ 1.6
2.1 1) 2)
Product composition , 5 12th 9
5.8 . χ wall- - "-—-""
Bitumen! Solid ' lunq oil': 86 14th 1.1 2.4 ·. s
I.
Ge 220 6.0
2.8 4.6 0.7 Solid ⁴ gas , 7
, 7 1.8
7.8 12th 4.7 75
77 25th
23 - weight
balance sheet cn
ο
to 221
222. 4.6 7.5
9.4 2.2
0.9 26th
35 , 4 - 15-
19th 1.8 77 23 101.7
98.9 - 00
Crt 223 0.9
3.8 6.1 1.6 33 , 2 - - 4.5
1.8 68 32 - · ·. _ 106.5 ' O / O70 224 4.5 20.6 l _f 6 36
37 ,1 • ίο - - 67 33 0.3 - 99.1
100.9 cri 225 3.3 4.8 37 , 0 6th 12th - 72 28 1.8 0.6 0.45 100.6 226 4.0 6.5 2.4 13th • 13 2.6 2.3. 2, .7 99.5 3.0 26th 5 100.3 36 99.9 iro
cn

2)% by weight, based on the coal feed material, on a moisture-free basis.

3)% by weight, based on the particular product fraction, on a moisture-free basis.

4) including the catalytic converter, if present. ':

- Ill -

The above examples are intended to illustrate the process according to the invention without restricting it. The different components' of the catalyst system in the process according to the invention do not have exactly the same effectiveness. The best Selection of these components and their concentrations and the other reaction conditions depend on the particular carbonaceous material to be processed.

609850/0705

Claims (49)

Claims 1. Process for the recovery of hydrocarbon products with improved quality from carbonaceous material, such as from oil shale solids, tar sand solids, coal solids, and / or a hydrocarbon fraction containing paraffins, olefins, olefin equivalents or acetylenes as such or as substituents on ring compounds, thereby characterized in that the carbonaceous material is treated with a water-containing fluid material, the density of the water in the water-containing fluid material being at least 0.10 g per ml and wherein sufficient water is present in the water-containing fluid material to be used as v / to serve as an effective solvent for the recovered hydrocarbons, and being at a temperature in the range of about 316 ° C (600 ° F) to about 482 ° C (900 ° F) in the absence of externally supplied hydrogen and either in the absence of or - Presence of an externally added catalyst system tet, such as a sulfur-resistant catalyst, such as at least one basic metal carbonate, basic metal hydroxide, transition metal oxide, oxide-forming transition metal salt and / or mixtures thereof, and / or a catalyst system which contains a sulfur- and nitrogen-resistant catalyst, such as at least a soluble or insoluble transition metal compound, a transition metal deposited on a support, and / or mixtures thereof. 2. The method according to claim 1, characterized in that the density of the water in the fluids containing water Material is at least 0.15 g per ml. 3. The method according to claim 2, characterized in that the density of the water in the fluids containing water Material is at least 0.2 g per ml. 509850/0705 4. The method of claim 1 wherein the temperature is at least 374 ° C (7O5 ° F). 5. The method according to claim 1, characterized in that the carbonaceous material is treated with the water-containing fluid material for a time in the range of about 1 minute to about 6 hours . 6. The method according to at least one of the preceding claims, characterized in that carbonaceous Material with the water-containing fluid material for a time ranging from about 5 minutes to contacted about 3 hours. 7. The method according to at least one of the preceding claims, characterized in that the carbon-containing Material with the water-containing fluid material for a time in the range of about 10 minutes treated for about 1 hour. 8. The method according to at least one of the preceding claims, characterized in that the water containing fluid material is essentially water. 9. The method according to claim 1, characterized in that carbon solids are used as the carbonaceous material and that the hydrocarbon products are cracked and desulfurized with improved quality. 10. The method according to claim 9, characterized in that the weight ratio of coal solids to water in the water-containing fluid material is in the range of about 3: 2 to about 1:10. 11. The method according to claim 10, characterized in that the weight ratio of coal solids to water in the water-containing fluid material ranges from about 1: 1 to about 1: 3. 6098S0 / 070S 12. The method according to claim 9, characterized in that the coal solids have a corresponding maximum particle size 1.27 cm (1/2 inch) in diameter. 13. The method according to claim 12, characterized in that the coal solids have a maximum particle size accordingly 0.6 cm (1/4 inch) in diameter. 14. The method according to claim 13, characterized in that the coal solids have a maximum particle size of 2.38 mm (8 mesh). 15. The method according to claim 9, characterized in that the fluid containing water is an organic material such as biphenyl, pyridine, a highly saturated oil, an aromatic oil, a partially hydrogenated aromatic oil and / or a mono- or polyvalent compound contains. 16. The method according to claim 15, characterized in that the fluid material containing water is an organic Contains material such as biphenyl, pyridine, a highly saturated oil and / or a mono- or polyvalent compound. 17. The method according to claim 16, characterized in that the water-containing fluid material is a highly saturated Contains oil. 18. The method according to claim 1, characterized in that the carbonaceous material with the water containing fluid material either in the absence of an externally added catalyst system or in the presence an externally added sulfur-resistant catalyst is contacted, such as at least one basic metal carbonate, basic metal hydroxide, transition metal oxide, oxide-forming transition metal salt or mixtures thereof. ■ 509850/0705 19. The method according to claim 18, characterized in that the carbonaceous material is oil shale solids, Tar sand solids and / or a hydrocarbon fraction be used, the hydrocarbon fraction being paraffins, olefins, olefin equivalents or Contains acetylenes as such or as substituents on ring compounds and wherein the hydrocarbon products cleaved, desulphurized and demetallized with improved quality and essentially all of it Sulfur removed from the isolated hydrocarbons is removed as elemental sulfur. 20. The method according to claim 19, characterized in that the carbonaceous material is a hydrocarbon fraction is the paraffins, olefins, olefin equivalents or acetylenes as such or as substituents on ring compounds, and that the weight ratio of Hydrocarbon fraction to water in the water-containing fluid material in the range of about 1: 1 to about 1:10. 21. The method according to claim 20, characterized in that the weight ratio of hydrocarbon fraction to Water in the water-containing fluid material ranges from about 1: 2 to about 1: 3. 22. The method according to claim 19, characterized in that the carbonaceous material oil shale solid or Is tar sand solids and that the weight ratio of Oil shale or tar sand solids to water in the Fluid material containing water is in the range of about 3: 2 to about 1:10. 23. The method according to claim 22, characterized in that the weight ratio of oil shale or tar sand solids to water in the water-containing fluid material in the range of about 1: 1 to about 1: 3 lies. 509850/0705 24. The method according to claim 22, characterized in that the oil shale solids have a maximum particle size 1.27 cm (1/2 inch) in diameter. 25. The method according to claim 24, characterized in that the oil shale solids have a maximum particle size 0.6 cm (1/4 inch). 26. The method according to claim 25, characterized in that the oil shale solids have a maximum particle size of 2.38 mm (8 mesh). 27. The method according to claim 18, characterized in that the carbonaceous material with the water-containing fluid material in the absence of an externally supplied one catalytic system is treated. 28. The method according to claim 18, characterized in that the carbonaceous material with the water containing fluid material is treated in the presence of an externally supplied sulfur-resistant catalyst, such as at least one basic metal carbonate, basic metal hydroxide, transition metal oxide, oxide-forming transition metal salt and / or mixtures thereof. 29. The method according to claim 1, characterized in that the carbonaceous material with the water-containing fluid material in the presence of an outside added catalyst system is treated, which is a sulfur- and nitrogen-resistant catalyst, such as at least one soluble or insoluble transition metal compound, a transition metal deposited on a support, or mixtures thereof, contains and wherein essentially all of the sulfur removed from the recovered hydrocarbons is in the form of elemental sulfur is removed. 609850/0705 30. The method according to claim 29, characterized in that the catalyst used is ruthenium, rhodium, iridium, osmium, Palladium, nickel, cobalt, platinum or mixtures thereof are used. 31. The method according to claim 30, characterized in that there is used as catalyst.Ruthenium, rhodium, iridium, osmium or mixtures thereof are used. 32. The method according to claim 29, characterized in that the catalyst is present in a catalytically active amount which is equivalent to a concentration level in the water-containing fluid material in the Range from about 0.02 to about 1.0% by weight. 33. The method according to claim 32, characterized in that the catalyst is present in a catalytically effective amount which is equivalent to a concentration level in the water-containing fluid material in the Range from about 0.05 to about 0.15% by weight. 34. The method according to claim 29, characterized in that the catalyst system additionally includes an activator or Accelerator contains, such as at least one basic metal hydroxide, one basic metal carbonate, one transition metal oxide, an oxide-forming transition metal salt or mixtures thereof, and wherein the activator has the activity of the catalyst reinforced. 35. The method according to claim 34, characterized in that the transition metal in the oxide and salt from the group the transition metals of groups IVB, VB, VIB and VIIB of the periodic table. 36. The method according to claim 35, characterized in that the transition metal in the oxide and salt from the following Group is selected: vanadium, chromium, manganese, ?: ir.en, titanium, molybdenum, copper, zircon, niobium, tantalum, Rhenium unci / or tungsten. 509850/0705 37. The method according to claim 36, characterized in that the transition metal in the oxide and salt from the group 'which contains: chrome, hangan, titanium, tantalum and tungsten. 38. The method according to claim 34, characterized in that the metal in the basic metal carbonate and hydroxide is an alkali metal and / or an alkaline earth metal. 39. The method according to claim 38, characterized in that the metal in the basic metal carbonate and hydroxide Is sodium and / or potassium. 40. The method according to claim 34, characterized in that the ratio of the number of atoms of the metal in the Activator to the number of atoms of the metal in the catalyst ranging from about 0.5 to about 50 lies. 41. The method according to claim 40, characterized in that the ratio of the number of atoms of the metal in the Activator to the number of atoms of the metal in the catalyst ranging from about 3 to about 5 lies. 42. The method according to claim 29, characterized in that the carbonaceous material is oil shale solid, Tar sand solids and / or a hydrocarbon fraction is used, the paraffins, olefins, olefin equivalents or acetylenes as such or as substituents on ring compounds and that the hydrocarbon products with improved quality split, hydrogenated, desulphurized, demetallized and from nitrogen are freed and that essentially all of the sulfur from the recovered hydrocarbons is removed, is removed in the form of elemental sulfur. 509850 / 070S 43. The method according to claim 42, characterized in that a hydrocarbon fraction is used as the carbonaceous material is used, the paraffins, olefins, olefin equivalents or acetylenes as such or as substituents on ring compounds and that the weight ratio of hydrocarbon fraction to water in the water-containing fluid material ranges from about 1: T to about 1:10. 44. The method according to claim 43, characterized in that the weight ratio of hydrocarbon fraction to water in the water-containing fluid material in the range of about 1: 2 to about 1: 3 lies. 45. The method according to claim 42, characterized in that the carbonaceous material or oil shale Tar sand solids are used and the weight ratio from oil shale or tar sand solids to water in the water-containing fluid material in the Range from about 3: 2 to about 1:10. 46. The method according to claim 45, characterized in that the weight ratio of oil shale or tar sand solids to water in the water-containing fluid material in the range of about 1: 1 to about 1: 3. 7. The method according to claim 45, characterized in that the oil shale solids have a maximum particle size 1.27 cm (1/2 inch). 48. The method according to claim 47, characterized in that the oil shale solids have a maximum particle size 1/4 inch. 49. The method according to claim 48, characterized in that the oil shale solids have a maximum particle size of 2.38 mm (8 mesh). 5098S0 / O70S - Blank page