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    • 专利摘要:
    1. A METHOD FOR PRODUCING HYDROCARBON FRACTIONS FROM CARBON-CONTAINING RAW , in order to increase the yield of the target products, the feedstock is brought into contact with water with a density of 0.1-0.7 g / MP in case it is gas oil and residual products, at 374-482, in case it is oil sands rocks and coal, at a temperature of 315-482 s, or, if they are oil-bearing shale, oil-bearing sandy rock, coal, gas oil, and residual oil products, at a temperature of 315-482 C in the presence of an additionally introduced catalyst containing metal carbonates, metal hydroxides and transition metal compounds, and the process is carried out at a pressure of 211-1055 kg / cm.
    公开号:SU1029830A3
    申请号:SU752144453
    申请日:1975-05-30
    公开日:1983-07-15
    发明作者:Дэвид Макколлам Джон；Майкл Квик Леонард
    申请人:Стандарт Ойл Компани (Фирма)；
    IPC主号:
    专利说明:

    2. Method of pop, 1, characterized in that when using coal as a raw material, water is used that contains an additive of an organic solvent at a weight ratio of water to solvent equal to 2.25-17: 1.
    3. A method according to claim 2, characterized in that diphenyl, pyridine, oily fractions are used as an organic solvent.
    4. Method according to claims, 1-4, characterized in that the process
    (Conducted in the presence of a sulfur-resistant catalyst selected from the group consisting of alkali metal carbonate, alkali hydroxide, tal, oxide, or an oxidizing salt of the metal 1УВ, УВ, У1В and OVG groups of the Periodic System of Elements or their combinations.
    5 The method according to paragraphs. 1-4, characterized in that the process is carried out in the presence of a sulfur- and nitrogen-resistant catalyst: a metal chloride selected from the group consisting of ruthenium, rhodium, iridium.
    osmium, palladium, nickel, cobalt, platinum, or combinations thereof.
    6. The method according to claim 5, characterized in that the process is carried out in the presence of a catalyst containing a promoter selected from the group consisting of alkali metal carbonate, alkali metal hydroxide, oxide or an oxidizing salt of metal 1УВ, УВ, У1В, UPV groups of the Periodic system elements or their combinations.
    7. Method according to paragraphs. 1-6, that is, that the process is carried out at a contact time of 0.015 6, 0 h.
    8. Method according to paragraphs. 1-7, that is, when using gasoil and residual oil products as a raw material, the process is carried out at a feed: water ratio of 1: 1-1: 10, when using oil shale, oil bearing sand, coal - at a feed ratio : water 3: 2-1: 10.
    The priority on paragraph 31.05.74 in PP. 1, 4-8
    07/01/74 in paragraphs 2.3
    one
    This invention relates to methods for producing hydrocarbon fractions from carbonaceous feedstocks and can be used in the oil-producing and oil-processing industries.
    A promising method for separating hydrocarbons from carbon-containing raw materials is extraction with a dense liquid, the latter being a liquid or a dense gas, the density of which approaches the density of the liquid. The extraction process with a dense fluid depends on changes in the properties of the fluid, in particular on the density of the fluid, which varies with pressure. At temperatures below its critical temperature, the density of the fluid changes stepwise with pressure. Such sharp drops in density are associated with interfacial | vapor-liquid transitions. At temperatures above the critical temperature of the temperature of the liquid, its density increases almost linearly: It occurs with increasing pressure according to the law for ideal gases, although deviations from linearity are noticeable at higher pressures. Such deviations are more noticeable when the temperature is approaching, but all
    still lying above its critical temperature.
    At a given pressure and temperature, the value of which is higher than the critical temperature of the compressed fluid, the dissolving capacity of the compressed fluid must be greater, the lower the temperature. At a given temperature lying above the critical temperature of the compressed fluid, the dissolving capacity of the compressed fluid should be the greater, the higher the pressure. Although these are important parameters that affect solubility.
    act above the critical temperature of the solvent liquid, however it is not necessary to maintain the solvent phase at a temperature above the critical one. It is sufficient that the liquid solvent is maintained at sufficiently high pressures and its density is high.
    The basis of the separation process is extraction with a dense liquid at
    at elevated temperatures, the substrate is contacted with a dense, compressed liquid at elevated temperatures, as a result of which the substrate material dissolves in the liquid phase, and the liquid phase containing this dissolved material is then separated and decomposed to the point where the dissolving liquid capacity and the material dissolved in it is separated in the form of solid sediment or a new liquid phase.  Based on the conditions of high solubility of substances in dense, compressed liquids, some general conclusions were obtained based on empirical dependencies.  For example, the dissolving ability of a dense, compressed liquid depends on the physical properties of the liquid solvent and the substrate material.  On the basis of this, it can be assumed that liquids of different chemical nature, but with similar physical properties, have the same properties as, for example, compressed ethylene and compressed carbon dioxide.  By analogy with the usual separation processes, various variants of | the construction of a dense liquid can be carried out. For example, both the extraction stage and the decompression stage provide ample opportunities for effecting the separation of mixtures of various risches.  Dp extraction of more volatile materials may be created under conditions that are more volatile, and extraction of less volatile materials may be conducted under more severe conditions.  The decompression can be carried out in one or several stages to separate the less volatile compounds first.  The degree of extraction and the release of the product during decompression can be adjusted by selecting the appropriate liquid solvent, by setting the appropriate temperature and injection pressure or decompression, and by changing the ratio between substrate and liquid solvent loaded into the extractor.  Thus, extraction with a dense liquid at elevated temperatures can be considered as a rectification option as an extraction with liquid solvents at lower temperatures.  The main advantage of the extraction of a dense liquid before distillation is the possibility of using substances with low volatility.  Based on the extraction with a dense liquid, it is also possible to suggest a variant of molecular distillation, but with such high concentrations in the dense liquid phase, which will lead to a significant increase in productivity.  The extraction of dense liquids is particularly valuable for processing temperature-sensitive substances since the extraction in the phase of dense liquids can take place at temperatures well below the temperatures required for the distillation process.  The advantage of extraction with a dense liquid at elevated temperatures as compared with liquid extraction at lower temperatures is that the dissolving capacity of the compressed liquid solvent can be continuously adjusted by maintaining a certain pressure, not temperature.  The ability to adjust the dissolving capacity by changing the pressure makes it possible to approach the solvent extraction process in a new way and with a different scale.  Methods are known for producing hydrocarbon fractions from carbon-containing feedstock using solid liquid extraction principles.  For example, methods for separating liquid hydrocarbon fractions from a hydrocarbon containing feedstock include the use of water.  Thus, a method is known for separating oil from oil shale, in which, raw materials. steam is treated at 371-482С and pressure 70-210 kg / cm.  Oil is extracted from oil shale in the form of vapors mixed with water vapor ClJ.  There is a known method for dissolving bituminous coal by heating a mixture of bituminous coal, hydrogen masonor, carbon monoxide, water and alkali metal hydroxide at 400-450 ° C and a total pressure of at least 280 kg / cm 2.  A method is known for producing hydrocarbon fractions from coal, which involves contacting the crushed coal with water, at least part of which is in the liquid phase, by externally acting with a reducing gas, a compound selected from aym acid and carbonates, and an alkali metal hydroxide under conditions of liquefaction at 200370 ° C 3.  A multistep process is known for hydrotreating heavy hydrocarbon fractions to extract and / or reduce the concentration of sulfur-containing, nitrogen-containing, organometal and asphaltenic impurities, the stages include pretreatment 5 / hydrocarbon fraction in the absence of a catalyst with a mixture of water and hydrogen supplied from outside at a temperature above the critical water temperature and pressure at 70 kg / cm2; contacting the resulting liquid product with externally supplied hydrogen under hydrotreating conditions and in the presence of catalyst mixture.  A method is known for producing hydrocarbon fractions from carbonaceous material (whole raw material - heavy hydrocarbon oils, residual hydrocarbon fractions, solid carbonaceous materials by contacting the raw material with a catalyst, based on nickel - spinel, promoted by a barium salt organic organic in the presence of steam.  Process temperature 216-538 s, pressure - 14210 kg / cm I.  A method of producing hydrocarbon fractions is known by introducing water and a catalytic system containing at least two components into the feedstock.  Water may be contained in a natural hydrocarbon. fractions water or may be added to the hydrocarbon fraction from an external source.  The volume ratio of water: hydrocarbon in such a fraction is preferably 0.1-5.  The first of the components of the catalytic system promotes the formation of waterborne, the second reaction between the generated hydrogen and the constituents of the hydrocarbon fraction. The process is carried out at 400-455 C, a pressure of 21-280 Kr / CM f6J.  Closest to the invention is a method for producing hydrocarbon fractions from carbonaceous feedstock — oil shale by contacting the latter with water taken in a large amount and / by weight approaching the weight of the shale.   The process temperature exceeds 260 ° C, the pressure is above 70 kg / cm, the optimum yield of the desired product is obtained at 371 ° C, pressure of 210 kg / cm-g.  The disadvantage of this method is the relatively low yield of hydrocarbon fractions.  The purpose of the invention is to increase the yield of target products.  This goal is achieved in that according to the method of producing hydrocarbon fractions from carbon-containing raw materials selected from the group including oil shale, oil sands, coal, gas oil and residual oil products, by bringing the raw material into contact with the raw material raw materials are brought into contact with water with a density of 0.1-0.7 g / ml at 374-482 ° C, if the raw material is gas oil or residual oil products, or at 315-482 ° C.  if the raw material is oil-bearing sandy rocks and "amenal coal, sludge at 315-482 ° C in the presence of an additionally introduced catalyst containing metal carbonates, metal hydroxides and metal compounds of the transition group, if oil-bearing shale, oil-bearing sandy rocks, stone coal, gas oil and residual oil products, the process is carried out at a pressure of 211-1055 kg / cm.  When using coal as a feedstock, the latter is contacted with water containing an additive of an organic solvent at a weight ratio of water to organic solvent of 2.25-17: 1.  Biphenyl, pyridine, oily fractions are used as an organic solvent.  The process is carried out in the presence of a corrosion-resistant catalyst selected from the group comprising silk-wool carbonate, alkali metal hydroxide, oxide or an oxidizing salt of metal 1УВ, УВ, В1В and OV groups of the Periodic system of elements or their combinations.  The process is carried out in the presence of sulfur and nitrogen-resistant metal chloride catalyst selected from the group containing ruthenium, rhodium, iridium, osmium, palladium, nickel, cobalt, platinum, or a combination of these.  In the latter case, it is possible to use a catalyst containing a promoter selected from the group comprising an alkali metal carbonate, an alkali metal hydroxide, an oxide or an oxidising salt of metal 1УВ, УВ, УВ, В1В groups of the Periodic system of elements or their combination.  Preferably, the process is carried out at a contact time of 0.015-6.0.  When gas oil and residual oil products are used as raw materials, the process is carried out with a raw material: water ratio of 1: 1-1: 10, using oil shale, oil bearing sand, coal - with a raw material: water ratio of 3: 2-1: 10.  According to the method, it is necessary to use a sufficient amount of water so that in a dense phase containing water, there is an amount of it that is sufficient to serve as an effective solvent for the liberated hydrocarbons.  Water contained in the dense phase may be in the form of liquid water, or in the form of dense gaseous water.  The water vapor pressure in the dense phase containing water must be maintained at a level high enough so that the density of water in the dense phase containing water is at least 0.1 g / ml.  So, with the limitations due to the size of the reactor used in this work, the weight ratio of hydrocarbon smr, besides specified below, to water in a dense phase, preferably 1: 1-1: 10, more preferably 1: 2-1: 3 .  Similarly, the preferred weight ratio of oil shale, oil sand or coal to water in a dense phase containing water is 3: 2-1: 10, more preferred 1: 1-1: 3.  The addition of an organic compound, such as biphenyl, pyridine, a partially hydrogenated aromatic oil, or a mono- or polyatomic compound, such as methyl alcohol, expands the solubility limits and the dissolution rate of hydrocarbons in the dense phase. Thus, subsequent cracking, hydrogenation, desulfurization, dimethylization and denitrification, can be easier.  In addition, a compound other than water in the phase containing water may be a source of hydrogen, for example, when reacting with water.  When using a sulfur and nitrogen resistant catalyst selected from the group comprising at least one soluble or insoluble transition metal compound, or a transition metal on a carrier, or a combination thereof, the concentration of such a catalyst is preferably 0.02 to 1.0% by weight of water contained in a dense fluid. If such a catalyst does not dissolve in a liquid containing water, then it can be added as a solid and suspended in the reaction mixture. The catalyst can also be deposited on a substrate and suspended in a water-holding liquid.  Charcoal, activated carbon, alundan and oxides such as silicon oxide, alumina, magnesium dioxide and titanium dioxide can be used as carriers.  When using a sulfur-resistant catalyst, selected from the group comprising at least one basic metal carbonate, basic metal hydroxide, oxide of the transition metal, oxidation-forming salt of the transition metal or their mixture, the concentration of the latter is 0.013, 0 wt. %, preferably 0.10-- 0.50% by weight of water.  Such a catalyst may be introduced as a solid compound and suspended in the reaction mixture or as a water soluble salt, for example, manganese chloride or potassium permanganate, which, under the conditions used according to the invention, forms the corresponding oxide.  The catalyst may also be deposited on a substrate and used as such in a stationary layer scheme or suspended in a liquid containing water.  The method according to the invention may be carried out batchwise or continuously.  Examples 1-38.  Illustrate the periodic processing of oil shale, oil sands under various conditions.  In each case, the experiment was carried out as follows (unless otherwise indicated).  Oil shale or oil sand feed, water and, if used, components of the catalytic system are loaded at ambient temperatures into a 300 ml batch autoclave, in which the reaction mixture is mixed.  The components of the catalytic system are introduced in the form of aqueous solutions or aqueous suspensions of solids.  Except where otherwise indicated, in each of the examples the required amount of water is introduced so that at a temperature, pressure of the reaction and used reaction volume its density is 0.1-0.7 g / ml.  The autoclave is flushed with an inert gas of argon, then closed &  The same inert gas is introduced to raise the pressure in the reaction system.  Then the temperature of the reaction system is raised to the desired level, a dense liquid phase containing water is formed.  To increase the temperature in the aktoklav from ambient temperature to 349 ° C, it takes 28 minutes (about 6 minutes to raise the temperature from 349 to about 6 minutes to raise the temperature from 371 to C99c).  Once the desired temperature is reached, it is kept constant for the required period of time.  The final temperature and time to maintain it are determined by the reaction temperature and the reaction time, respectively.  As the reaction proceeds, the pressure in the reaction system rises.  The pressure at the beginning of the reaction is defined as the reaction pressure.  Then the dense liquid phase is subjected to decompression and quickly distilled from the reactor, while removing gas, water to oil.  Bitumen remains in the reactor, inorganic bring and components of the catalytic system, if it is present.  The oil implies a liquid hydrocarbon fraction boiling at or below the reaction temperature, the bitumen is a hydrocarbon fraction, which is higher than the reaction temperature, the organic residue is burnt lanes or burnt oil-bearing sand.  Gas, oxen and oil are trapped in a pressure vessel cooled with liquid nitrogen.  The gas is removed by heating the vessel to room temperature and then analyzed on a mass spectrum using gas chromatography and infrared spectrum.  Water and oil are blown out of the high pressure vessel with compressed gas, as well as simultaneous heating.  Water and oil are then separated by decantation.  The oil is analyzed for its sulfur and nitrogen content and its density and specific gravity are determined.  I The bitumen, the inorganic residue and the components of the catalytic system, if used, are washed out of the reactor with chloroform.  The solid residue is separated from the solution containing bitumen by filtration.  Bitumen is analyzed for its sulfur and nitrogen content.  The solid residue is analyzed for its inorganic carbonate content.  Oil shale from the Colorado field is used as oil shale.  Pieces of shale are crushed and sieved to obtain fractions with different particle sizes.  For definition, content. kerogen in these fractions part of each fraction is calcined in air for 30 days to remove water and kerogenic hydrocarbon containing material without decomposition of inorganic carbonate.  The particle size of the oil shale samples used in the experiments and the percentage of weight loss during the calcination process of each of these samples are presented in Table 1, Examples 1-37 illustrate periodic processes for producing carbohydrate genera from oil shale samples presented in Table 1, All experiments conducted in a 300 ml autoclave.  The experimental conditions and the results obtained in these examples are presented in Tables 2 and 3, respectively.  In experiment no. B (table 2), the residual product of experiment 5 is used after the separation of gas, water and oil. In experiment no. 36, water additionally contains RuC1 (1-3) HjO in an amount of 0.1 weight and 0.6 weight. % sodium carbonate. In experiment 37, water additionally contains 0.6 wt.% sodium carbonate. In addition to Torg, the analysis of the products (see, Table 3) is combined for examples 5 and 6.  Oil fractions have a density of 0.92-0.94 g / ml. Bituminous fractions have HocTb / wlfOl g / ml density and beats, weight approximately. Oil shale sample A contains 0.1 weight,% sulfur, 1.7 weight,% Nitrogen As can be seen from the results of the experiments, the use of the catalyst in Example 36 leads to an increase in the yield of the oil fraction relative to the amount of the bitumen fraction obtained and to a decrease in the sulfur content in the products.  The use of the catalyst in Example 37 also leads to an increase in the amount of oil fraction relative to the amount of generatrix from the bituminous fraction.  The results of elementary analyzes of several samples of oil and bitumen fractions obtained from some examples, as well as oil-bearing shale raw materials and oil-rich kerogen product obtained using thermal cracking in the retort are presented in Table 4. These data indicate that the elemental compositions oils from different oil shale are the same.  The weight data for the combined oil and bitumen fractions obtained in Examples 7-11 indicate that the combined fractions have the same nitrogen content, but lower sulfur content compared to oil obtained by thermal cracking in the retort.  The ratios of the number of H / C atoms for the oils obtained by this method and for the oils obtained by thermal cracking in the retort are the same.  However, the H / C atom ratio for the combined oil- and bitumen fractions obtained by the first route is less than this ratio for the oil, t, e, of the total amount of liquid products obtained by thermal cracking in the retort.  This indicates a higher overall yield of the LIQUID fraction obtained by this method compared with thermolytic distillation. The results of the analysis of the combined oil fractions obtained in Examples 7-11 are presented in Table 5, along with similar results for oil fractions obtained from oil shale by known methods by thermal cracking in the retort and gas combustion in the retort,. The content of olefins in the oil fraction boiling at a temperature up to that obtained by this method differs from the content of olefins in the oil fraction boiling up to that obtained by burning gas in the retort and during thermal cracking in the retort.  The olefin content in this fraction is about two times lower than the olefin content.  in the corresponding fractions obtained by thermal and gas cracking in the retort.  This indicates that this process produces hydrogen, which is partially consumed in the hydrogenation of the olefins produced.  There is a certain equilibrium between the hydrocarbon content in oil shale samples, a certain removable method and the weight content of hydrocarbons in such samples, taking into account the weight loss of the latter during calcination in air for 30 minutes.  The volume and weight content of hydrocarbons is calculated by the Fisher method.  This dependence is shown in FIG.  one.  Based on the use of dependencies, the expected hydrocarbon yields from oil shale samples used in the experiments were evaluated to compare the actual hydrocarbon yield with the expected possible total hydrocarbon output from the oil shale samples used.  . The weight loss during the calcination of oil shale samples and the dependence shown in FIG.  1, indicates that the used samples of oil shale give liquid products in the range of about 14-22 weight. % of oil shale feedstock.  FIG.  Figure 2 shows the actual weight loss in the process of calcining sample A of oil shale, the expected yield of hydrocarbons from this sample of oil shale, and the actual yields of oil, bitumen and gaseous carbon dioxide and Cd hydrocarbons obtained in 2-hour periodic experiments using sample oil shale at different temperatures.  These experiments were carried out using the weight relationships of shale: water 0.56 or 1.  In this case, when the ratio is 0.56, 90 g of water is charged.  When this is a ratio of 1, then the water load is 60 g. Pressure 178.5-294 kg / cm.  The data shown graphically in FIG.  2 are taken from the results presented in Table.  3  Liquid selectivity — the ratio of the total yield of liquid products to the weight loss of oil shale sample during the calcination process — for sample A of the oil shale at 0.67.  Oil selectivity — the ratio of oil yield to total liquid product yield — for sample A of the oil-bearing layer at 450 ° C is 0.61.  The yield of oil obtained from oil shale by this method largely depended on the temperature.  The overall yield of liquid products (oil and bitumen) was relatively constant with tecteratures and sharply dropped at temperatures below 347 ° C.  At temperatures above, the total values of the liquid products slightly exceed those of the products as determined by the Fisher method.  At this temperature, the lighter hydrocarbon fractions continued.  From FIG.  2 it follows that a sharp increase in the oil yield and a decrease in the yield of bitumen occurs with a rise in temperature above 37 ° C.  Such an increase in the yield of oil and a decrease in the yield of bitumen is quite likely if the cracking of bitumen is thermal or catalytic in the presence of catalysts in the oil-bearing shale itself.  Similar results are presented in table.  6, obtained in examples 1, 2, 15 and 26-28 with different contact times.  These data indicate that even at a temperature of 70 ° C (slightly below the critical temperature of water), the selectivity values of the liquid and water significantly decreased compared with the values obtained at temperatures above the critical temperature of water.  Results showing the effect of oil shale particle size on the rate of hydrocarbon release are shown in FIG. .  3 and 4.  The plots in FIG.  3 and 4 are obtained on the basis of the results presented in table. 3 for experiments, including the weight ratio of shale to water is 0.56.  The weight loss during the calcination process, the expected yield of hydrocarbons from the oil shale sample, and the measured yield of liquid hydrocarbon products are shown in FIG.  3 in the form of a contact time dependence on the size range of oil shale particles.  In the case of oil shale with a particle size of approximately 0.637 cm in the range and below more than 90 weight. The% carbon-containing materials contained in the raw materials are released in less than half an hour.  When pa3Nffip particles are equal to or less than 8 mesh, the total yield of liquid products is greater after a contact time of half an hour compared to a contact time of 2 hours and exceeds the expected yield of hydrocarbons from oil shale.  For such a raw material, the deviation of the total yield of liquid hydrocarbon products with an increase in contact time corresponds to an increased conversion of liquid products to dry gas, for example, when cracking liquid products.  The cracking flow is also indicated by the graphs in FIG.  4, which show the dependence of the selectivity of oil on the contact time and range of oil shale particles.
    When the particle size of the oil shale feedstock is within the range of 0.637-0.313 cm, the release rate is quite low, so that the total yield of liquid products after a contact time of half an hour is less than the total yield of liquid products after a contact time of 2 hours (Fig. 3).
    Thus, when using large particles, the ratio of surface area to volume of particles for such materials will be less than Yio compared to this ratio for thinner materials, the diffusion of water into coarser oil shale particles and the dissolution rate of the inorganic matrix in supercritical water may decrease. may decrease the rate of release of liquid products.
    The efficiency of separating liquids from oil shale by this method is associated with the partial dissolution of the inorganic matrix of the shale substrate. Thus, after complete separation of liquids from oil shale ores with a particle size in the range from 0.637 cm in diameter to 9 mesh, the extracted shale residue has significantly smaller particle sizes (usually within less than 100 mesh). In addition, a decrease in bulk density from 2.1 for raw materials to 1.1 g / ml for residual is also observed. When liquids are not completely separated from the oil shale feed, the oil shale particles retain most of the original conformation.
    High carbon dioxide yield when extracting liquid hydrocarbons from oil shale even at relatively low temperatures (349 ° C indicates decomposition of inorganic carbonates in the oil shale structure. Approximate balance of oil shale feed and the combined products recovered in examples 7-11 And oil shale shows that carbon dioxide is formed from inorganic carbonate (see Table 7).
    Dependencies based on which the products are characterized are presented below. The total amount (S ,,) of oil shale feed, excluding the water containing one degree in it, is defined as S.Q S + 1, + K, where the meaning of the symbols used is the same as that defined in Table 7.
    When the oil-bearing shale feedstock is titrated with acid, the amount of acid-titrated inorganic carbonates present in the feedstock 1 is determined, and thus the relationship between the measured amount of acid-titrated inorganic carbonate present in the initial feedstock and the measured amount of oil-bearing shale feed can be established. For sample A of oil shale, this dependence has the form 1 0.187So.
    After calcining the oil shale feed in air for 30 minutes at 538 ° C, all organic compounds are removed and the measured weight of all inorganic compounds can be expressed, based on the total amount of oil shale feed, as follows: S 0.678So.
    Calculated from the last two equations, S is 0.491So., Solid products, obtained 1 after the separation of hydrocarbons from the oil-bearing shale raw material by this method, S + xXc 0.686So,
    When conducting this experiment, the following conditions are used: temperature 400 ° C, pressure about 280 kg / cm time 2 .4, water load 60 g and weight ratio of shale: water 1.0.
    By titrating with the acid of the solid residue of the waste shale, you can determine the amount of acid titrated by the inorganic carbonate present in the waste shale at the end of the experiment. The dependencies between the measured amount of inorganic carbonate acid titrated by the acid present after the removal of the coal is measured by the total
    hydrogens
    the amount of oil shale is of the following form x, O.IjySc, where X is part of the initially present amount of I, which still remains.
    By calcining the remainder of the waste oil shale in air for 30 minutes at 538s, all organic compounds are removed and the measured weight of the total amount of organic material remaining after the removal of hydrocarbons can be expressed, based on the total amount of oil shale, as follows S + xl 0, ,
    The calculated S value in the last two equations is 0.4965 r. This value corresponds to the value of S, calculated according to the analytical characteristics of oil-shale raw materials.
    From the data presented in table. It follows that the amount of acid-titrated inorganic carbonate in the remainder of the waste shale is significantly lower compared to the amount of inorganic carbonate acid-titrated in the oil-bearing: shale raw materials and the difference between these quantities can be attributed to 50-60% by weight of the resulting carbon dioxide. The carbon dioxide emitted from the kerogen in the oil-bearing slack feedstock can also be attributed to some residue. Inorganic carbonate in the structure of oil shale withstands thermal processing if the temperature is at a level not exceeding. Thus, thermal or gas firing in the retort usually does not reduce the amount of inorganic carbonate titrated by the kilogram. Conversely, the amount of inorganic carbonate titrated by the acid in the oil shale structure decreases when this method is carried out. 8 shows the results of a 2-hour experiment conducted by a periodic method at 400 ° C, showing the effect of oil-bearing weight ratio, shale, solvent on the total liquid product yield and oil selectivity. Isolation of products ends under selected conditions, when the weight ratio of oil shale: solvent is in the range of about 1: 1-1: 2. This weight ratio allows the liquid to be transported and the cMecfe is compressed by oil shale — a thinner in such a way that it is possible to continuously process the slurry. Example 38 describes a periodic method for producing hydrocarbons from oil-bearing sandy raw materials under the following conditions: reaction temperature 4bos, reaction time 2 hours, reaction pressure 28V kg / cm and argon pressure 17.5 kg / cm. The power of the reaction system is a mixture of 40 g of oil-bearing sand and 90 g of water. The test was carried out in a 300 ml autoclave. Get gas (hydrogen, carbon dioxide and methane) and oil in quantities equal to 2 and 8% of the feedstock unit weight - 0,9494. The oil contains jm, nickel, and vanadium 2.7%, 45, and 30 h mph, respectively. The outputs of gas, oil, bitumen and solid products in this example are 2.5, 3.7, 3.4 and 86.5%, respectively, based on the feedstock, and indicate a complete extraction of hydrocarbons from oil-bearing sandy rocks. The total amount of gas of oil, bitumen and solid fractions and the separated water corresponds to,. wt.% from the original oil-bearing natural raw materials and water. Examples 39-192. Reflect the processes of periodic processing of various types of hydrocarbon raw materials under the conditions used according to this method and show that the latter is accompanied by effective cracking, desulphurisation and, if the carbon-containing material is oil shale or oil sands or hydrocarbon fractions containing paraffins, olefins, olefin equivalents or acetylenes as such or as substituents in aromatics, demetallation, and also that carbon Orod recoverable from oil shale, tar sand or rocks coals also krekiruyuts, hydrogenated, desulfurizuyuts, and demetalliziruyuts denitrifitsiruyuts. Unless otherwise specified, use the following experimental method. Hydrocarbons, water-containing liquids and components of the catalytic system, if used, are loaded at ambient temperature into an autoclave. The components of the catalytic system are introduced as solutions in a liquid containing water or in the form of solids suspended in a liquid containing water. Except where otherwise indicated, a sufficient amount of water is introduced in each example, so that at the reaction temperature and with the reaction volume used, the density of water is 0.1-0.7 g / ml. The autoclave is rinsed with an inert gas maker and closed. Argon is also used to increase the pressure in the reaction system. The proportion of argon in total pressure at ambient temperature is the pressure of argon. The temperature of the reaction system is then raised to the desired level, and a dense phase containing water is formed. It takes about 28 minutes to maintain the temperature from ambient to about. Approximately 5. min is required to increase the temperature from 349 to and also b min to raise the temperature from 371 to. Upon reaching the final value of the required temperature, it was kept constant for the required period of time. The final constant temperature and the gap at this temperature. defined as reaction temperature and reaction time. As the reaction proceeds, the pressure in the reaction system is forced. The pressure at the initial reaction time is defined as the reaction pressure. After the desired reaction time has elapsed at the required reaction temperature and pressure, the dense liquid phase containing water is decompressed and quickly distilled out of the reactor, removing the gas, liquid containing water and light ends, leaving the yellow ends catalyzing the catalyst if it is used and other solid compounds in the reactor; The light ends are the liquid hydrocarbon fraction boiling at or below the reaction temperature, the hard ends are the hydrocarbon fraction boiling at a temperature above the reaction temperature. Gas containing water, liquid and light fractions is captured in a high-pressure vessel cooled with liquid nitrogen. The gas is removed by heating the vessel to room temperature and then analyzed by mass spectrometry, gas chromatography, and infrared spectroscopy. The water-containing phase and light fractions are removed from the reactor using compressed air and simultaneously heating the reactor. The water-containing liquid and light fractions are then separated by decantation. The light fractions are subjected to gas chromatography. T yellow fractions and solid residues, including the catalyst, if present, are washed out of the reactor with chloroform, and the heavy fractions are dissolved in this solvent. The solids, including the catalyst, are filtered from the solution containing heavy fractions. After distilling off the chloroform from the heavy fractions, the light and the same fractions are combined. If the liquid containing water is not yet separated from the light fractions, it is separated from the combined light and heavy fractions by centrifugation and decantation. The combined, light and heavy fractions are analyzed for the content of nickel vanadium and sulfur in them, the ratio of C atoms is determined. / H and specific gravity. Water is analyzed for the content of nike and vanadium, and the solid residue - for the content of nickel, vanadium and sulfur. X-ray fluorescence is used to determine nickel, vanadium and sium. . Examples 39-41 show that the catalysts used according to this method are not subjected to poisoning with sulfur compounds. Three experiments were conducted each with carbon monoxide, taken in an amount of 24.5 kg / cm in 90 ml of water, in a 240-ml autoclave with a reaction time of 4 hours. Soluble trichloride, ruthenium in an amount of 0 gt, was used as a catalyst. «Е1, (1-3) На.О. In addition, in example 40 water contains 1 ml of thiophene. Condition the reactions and compositions of the products according to the experiments in the table below. 9. The presence of the sulfur-containing thiophene compound did not cause catalyst poisoning or water-gas shift inhibition. Example 42 shows that the catalytic system acts as a catalyst for the hydrogenation of unsaturated organic compounds. When analyzing products of contact, 15 g of 1-octene with 30 g of water in a 100 ml aktoklav for 7 hours at a pressure of 245 kg / cm and a pressure of argon of 56 kg / cm in the presence of a soluble RuCl catalyst (1-3) carbon dioxide was detected hydrogen, methane, octane, cis- and trans-2-octene, paraffin and olefins containing five, six and seven carbon atoms, which indicates a significant decomposition and isomerization of the skeleton, as well as a change in the location of unsaturation. When interacting 15 g of 1-octene and 30 g of water In the presence of 0.1 g of RUCI (1-3) for 3 h in the same reactor at the same temperature, the reaction pressure is 174 kg / cm and the pressure of argon is 14 kg / cm yield octane 40%, 75% yield of octane is obtained using the same reaction mixture and under the same conditions, but the reaction time is 7 hours and the reaction pressure is 243 kg / cm, the pressure of argon is 56 kg / cmH Examples 43-44 illustrate the processes, in which sulfur-containing compounds, for example thiophene and benzothiophane, are decomposed to hydrocarbons, carbon dioxide and elemental cejMJ. . Example 43 illustrates the interaction of the reaction mixture -12 ml of thiophene and 90 ml of water in a 240-ml autoclave in the presence of 0.1 g of soluble RuClj- (1-3) at temperature i. At a reaction rate of 350 ° C, a pressure of 221 kg / cm, the argon pressure was 45.6 kg / cm and a reaction time of 4 hours. As a result, hydrocarbons are formed. and 0.1 g of elemental solid sulfur without noticeable amounts, sulfur oxides or hydrogen sulfide. Example 44. 23 ml of a solution of 8 mol.% Thiophene, - (ie, about 3 wt.% Sulfur) in 1-hexane and 90 ml of water are loaded into a 240-ml autoclave and contacted in the presence of 2 g of a solid substrate from. alumina containing 5 wt.% ruthenium (equivalent to 0.1 g of Y and ScP1-3), at a reaction temperature, a pressure of 245 kg / cm, a pressure of argon of 42 kg / cm and a reaction time of 4 hours. Obtain 0.9% of hydrocarbon products, containing sulfur in the amount of 0.9% based on thiophene. This decrease in thiophene concentration corresponds to 70% desulfurization. Catalyst activity was changed during 4 consecutive experiments.
    Examples 45-52 illustrate the processing of samples of vacuum gas oil and residual fuels and show that the catalytic system effectively catalyzes the process of desulphurisation, demetallization, cracking and the production of hydrocarbon fractions. The compositions of the used hydrocarbon raw materials are presented in table. ten.
    The residual fuels used in these examples are indicated in table. 10 (A). In tab. 10 shows the composition of cheese used in the following examples.
    Examples 45-48 use vacuum gas oil, examples 49-50 use atmospheric oil residues (B), in example 51-52 use oil residues. Example 45 uses vacuum gas oil under the same conditions as in examples 46-48. , in the absence of a catalyst (given for comparison. Table 11 presents the conditions of the experiment, the composition of the product, the degree of extraction of sulfur, nickel and vanadium. Liquid products are characterized as low boiling or more boiling depending on whether they boil at the reaction temperature or lower or higher. In each of the examples The user reaction temperature was 378 ° C. The process is carried out in a 300-milliliter autoclave. ruthenium, rhodium, osmium k dbbavl dissolved in the form of soluble salts uC R C (1-3) .RhCI X SHijO and OZSTS respectively.
    The data table. 11 show that even as a result of thermal processing without the addition of a catalyst from an external source, substantial cracking occurs, enrichment and slight desulfurization of the hydrocarbon feedstock. In the case of a relatively high weight ratio of oil: water, the compositions of products obtained as a result of thermal processing and as a result of processing in the presence of a ruthenium catalyst are the same. At a lower weight ratio, the oil: water analysis of the products indicates a more extensive cracking in the presence of a ruthenium catalyst. . ,
    The data in Table 11 shows that even as a result of thermal processing, without the addition of a catalyst from an external source, significant cracking and enrichment occurs and slight desulfurization of the hydrocarbon feedstock. In the case of a relatively high weight ratio of oil: water, the compositions of the products obtained as a result of thermal processing and as a result of processing in the presence of a ruthenium catalyst are the same. At lower weight ratios
    Water analysis of products indicates a more extensive cracking in the presence of a ruthenium catalyst. Under similar conditions and in the presence of a ruthenium or rhodium-osmium catalyst, much more complete conversion of the liquid feed into gases and liquid products that boil at temperatures equal or lower than the reaction temperature occurs. Sulfur recovered as a result of desulphurization is in the form of elemental sulfur when the density of water is at least 0.1 g / ml, for example, when the weight ratio of oil: water is 0.2 or 0.3. However, when the density is less than 0.1 g / ml, it is when the weight ratio is oil: water is 5.4 or. 6, the sulfur is recovered in the form of hydrogen sulfide. This indicates a change in the mechanism of desulphurisation of organic compounds upon contact with the dense, water-containing phase, depending on the density of water, of a dense, water-containing phase.
    Examples 53-54 illustrate the use of promoters of the catalytic system. Basic metal hydroxides and carbonates, oxides of transition metals, and, preferably, oxides of metals of groups IV, HC, WC and WC of the Periodic Table, do not have the catalytic action of processes associated with water phase transitions, but effectively increase the activity of the catalysts of the invention, which catalyze processes accompanied by water phase transitions.
    The promoter may be introduced as a solid and suspended in the reaction mixture or as a water-soluble salt, for example, manganese chloride or potassium permanganate, which, under the conditions of this method, forms the corresponding oxide. substrate and used as such in the process with a stationary layer or suspended in a liquid containing water. The assignment of the number of metal atoms in the permeation to the number of metal atoms is preferably 3-5.
    The product yields during the process, accompanied by water phase transitions, are a measure of promoting activity. In processes involving water phase transitions, hydrogen and carbon monoxide are formed by the interaction of a portion of the hydrocarbon feedstock with water. Formed with carbon monoxide reacts with water to form carbon dioxide and an additional amount of hydrogen. Then, the generated hydrogen in this way interacts with a certain part of the hydrocarbon feedstock to form the saturated compounds. In addition, some hydrocarbons are cracked in a hydrogen medium to form methane. The yields of hexane obtained from the processing of 1-hexene in Examples 53 and 54 are shown in FIGS. 5 and 6 with responsibly. In examples 53 and 54, the reaction mixture consists of 90 g of water and 17 ± 0.5 g of 1-hexene. The process is carried out for 2 hours in a 300 ml autoclave. FIG. 5 experiments in which the points labeled 1-5 were obtained were carried out at a pressure of u242, 238,, 242 and 246 kg / cm, respectively, and an argon pressure of 45.7; 45.7; About 43.5 and 43.5 kg / cm, respectively. In experiments corresponding to points designated 1-3, 0.2 g of manganese dioxide was used as a promoter; in experiments corresponding to points 4-5, the promoter was not used. FIG. 6 experiments for which points are obtained, indicated. -3, carried out at a reaction pressure of 197, 250 and 204 kg / cm, respectively, and pressure; argon 45.6 kg / cm. FIG. 5 shows an increase in the yield of hexane with the increase in the amount of a ruthenium catalyst either without a promoter or with the addition of 0.2 g of manganese dioxide. Similarly in FIG. B shows an increase in the yield of hexane with an increase in the amount of a pro-motor based on manganese dioxide and 0.1 g of RuCl3 1-3) H.2.0 catalyst. The graphs indicate that in the absence of a catalyst, one promoter does not have a catalytic activity in reactions involving water and the yield of hexane is less than 2 mol%, based on the feedstock. Also, for a given catalyst concentration, the addition of 0.2 g of promoter leads to a significant increase in the yields of hexane in the target product. Examples 55-68 show 2-hour batch experiments in a 300-ml autoclave containing RUCiv (1-3) and 0.2 g of oxides of various transition metals at. Argon pressure of 45.6 kg / cm in each example. Outputs g; eksana, carbon dioxide and methane are presented in, tab. 12 .. An increase in hexane output is observed in the case of all the oxides used, with the exception of barium oxide. When copper oxide is used, the output of hexane increases slightly. Thus, of all the promoters mentioned, effective promotion of the catalytic activity of the reactions involving water leads to the transition oxide group. . The ratio of methane release to carbon dioxide yield or to the output of hexane hydrocarbon feedstock is an indicator of the relative degrees to which competing hydrogen cracking reactions occur and the formation of hydrogen in reactions involving water. The results presented in table. 12 show that this promoter catalyzes cracking in a hydrogen environment and the formation of hydrogen in various degrees. Accordingly, by selecting one or another promoter, it is possible to adjust the selectivity of the reaction in the direction of cracking in a hydrogen medium or in the direction of hydrogen formation, as well as to roll over catalyst activity. The promotion of catalytic activity by oxides of transition metals is associated with chemical action, and not with surface effects. For this, an example 69 is conducted under the same conditions as. Example 55, but instead of the catalyst, 1 g of active carbon with a high specific surface area containing 5 wt.% ruthenium is used, i.e. 0.5 mmol of ruthenium, which is equivalent to 0.1 g of RuCl- (1-3) without a promoter. The specific surface area is 500 m / g. The yield of hexane is 12 mol.%, And the yield of carbon dioxide is 0.017 mol. These yields are less than the corresponding yields as defined in Example 55 in the presence of a promoter. Examples 70-76 show the changes in the degree of effectiveness of the various combinations of catalysts and promoters used in catalytic cracking, hydrogenation, skeletal isomerization, and double bond isomerization of hydrocarbon feedstocks. In each case, the hydrocarbon feedstock is a solution of 36 mol.% 1-hexene in a diluent for which benzene is used, with the exception of Example 74, where benzene is replaced by ethylbenzene. In each example, the reaction is carried out in a 300 ml auto; including clave. Under pressure of argon 45.5 kg / cm 1 reaction temperature, reaction time 2 hours. The composition of the raw material, the pressure, the composition of the catalysts, the yields of the products are presented in Table. 13. The high 1-hexene conversions in Example 70 reflect skeletal isomerization to methyl pentenes and double bonds to isomerization to 2- and 3-hexene, but in the case of a non-promoted catalytic system, the yield of hexane reaches only 26%. Adding a transition metal oxide, a transition metal salt, for example, pentachloride, tantalum, which, under the conditions used, form oxides, transition metals or a BASIC metal carbonate, cause a significant increase in the yield of hexane. None of the catalysts used in Examples 70-76 is effective in terms of cracking or hydrogenation of diluents, benzene and ethylbenzene. In the case when ethylbenzene is used as a diluent, only traces of dealkylated products, benzene and toluene are formed. Examples 77-83 indicate the relatively high efficiency of some components of the catalytic system used according to this method for catalyzing the cracking of apkylaromatics. In each example, the hydrocarbon feedstock was a solution of 43 small% 1-hexene and 57 mol.% Ethylbenzene. In each example, the hydrocarbon and water are contacted for 2 hours in a ZOO-mAl autoclave at a reaction temperature, argon pressure of 45.5 kg / cmH. The compositions used as feed, the reaction pressure, catalyst compositions and product yields are presented in Table. 14. . Although all of the catalytic systems used in Examples 77-83 are effective in terms of the catalysis process, water phase transitions, including 1-hexene, are involved, but only iridium and rhodium are effective from the point of view of ethylbenzene to benzene and toluol. Comparison of the yield of the products of Examples 80-82 indicates that the cleavage of apicalaromatics proceeds when using a catalytic system involving a combination of iridium or rhodium with one of the catalysts, but not pure iridium or rhodium. Examples 84-86 show that alkyl benzenes are split at ispol. This method with the same catalytic system as in Example 80, even in the absence of operability in a hydrocarbon feed. Each of these examples includes 2-hour flakes in a 300-ml autoclave conducted at a reaction temperature of 350 ° C and an argon pressure of 45.5 kg / cm. Hydrocarbon feed compositions, the amount of water added, the reaction pressure and the yields of alkyl aromatic products after cracking are listed . 15. Example 87 shows that hydrocarbon hydrocarbons can be cracked using the same catalytic system as in Example 80. In this driver, 15.9 g of n-geitane and 92.4 g of water are mixed in a 300-ml autoclave and heated. at a reaction temperature under a pressure of 217 kg / cm and a pressure of argon of 45.5 kg / cm during a reaction time of 2 hours. As a result, 0.67 g of methane is formed, which corresponds to 4.2 wt.% of n-heptane. The fact that only traces of products containing more carbon atoms than methane are found indicate that, if the hydrocarbon molecule disintegrates, then it decomposes to the end. Example 88-.117 illustrates the processing of oil sands in a 300-ml reactor. Properties of sandy rocks used in these examples are presented in table. 10. Deprived of light fractions DISTILLATES of oil-bearing sandy rocks are straight chain distillates of oil-bearing sandy rocks, the properties of which are also presented in Table. 1-0 (of the latter, it is necessary to remove another 25 wt.% Of light compounds). Straight chain DISTILLATES of oil-bearing sandy rocks are used as raw materials (feed mixes) in Examples 88-103; examples 104-117 use oil-bearing sand distillates deprived of light fractions as feed mixes. The conditions of the experiments and the results of the analysis of the products obtained in these examples are presented in table. 16 and 17. The reaction temperature in each example. Ruthenium, rhodium and osmium are added in the form of soluble salts (l-3) H, j, 0, and OsClr. respectively. Each component of the catalytic system in each example is added in the form of its aqueous solution or in the form of an aqueous suspension of the substance, depending on whether this component is dissolved in water. The amount of catalyst in the table. 16 are given in the same order in which the corresponding catalysts are listed. In tab. 17 data on percent sulfur recovery. Nickel and vanadium are obtained by analyzing the combined light and the same. Loy fractions. The weight balance is represented by the total weight percent of hydrocarbon feedstock, water, and catalyst. Comparison of the results presented in table. 17 shows that the formation of gas and solid residue and the degree of extraction of sulfur and metals increase with an increase in reaction time from 1 to 3 hours without introducing a catalyst. Adding a catalyst from an external source causes a small increase in the yield of solid residues of the specific product weights of the liquid product, but in the case of feed mixtures other than distillate oil-bearing
    sandy rocks have little effect on yields as a result of cracking in hydrogen and on the C / H ratio.
    In addition, a change in the oil-water weight ratio from 1: 3 to 1: 2 leads to a decrease in the recovery of sulfur and metals and a negative shift in the distribution of products. In the case of feed mixes, shifts are less negative with increasing weight ratio of hydrocarbon: water until 1: 1 ratio is reached.
    The results for heavier distillates of oil sands are similar to those for straight oil distillate sand distillates. The only difference is that the conversion of heavy fractions into light fractions for oil-bearing sandy sands lacking light fractions continued to increase — as the reaction time increased from 1 to 3 hours, while in the case of straight-chain oil distillate distillates such transformations ended in about 1h.
    The total yields and compositions of gas products obtained in a number of examples, the results of which are shown in Table. 17, are presented in table. 18.
    In all cases, the main component of the gaseous products is argon, which is also used to raise the pressure in the reactor and which is not presented in Table. 18.
    Changing the oil: water ratio from 1: 3 to 1: 2 and / or increasing the reaction time, it is possible to achieve an increase in gas yields. The addition of a catalyst also causes an increase in the yield of gaseous products.
    Based on the fact that among the gaseous products obtained in Examples 92, 93, 104, and 105 are carbon dioxide and hydrogen, it can be assumed that hydrogen and carbon monoxide are also formed without the addition of catalysts from external sources inherent in oil sands distillates and serving as catalysts.
    Comparison of the results presented in table. 17 shows that the addition of catalysts usually leads to a higher degree of desulphurisation compared with the case when the catalyst is not introduced from an external source. In addition, the addition of transition oxide, basic metal hydroxide or carbonate as such or as a promoter together with the catalyst of the process, accompanied by water phase transitions, significantly increases desulfurization. However, in the case of hydrocarbon feed mixtures other than oil distillate, the degree of desulphurisation decreases with increasing reaction time. In all cases, the sulfur extracted from the oil is elemental sulfur, and not carbon dioxide or hydrogen sulfide.
    Comparison of the results presented in table. 17 indicates that substantial metal recovery occurs even with a reaction time of less than 1 hour and in the absence of a catalyst introduced from an external source. However, the addition of a catalyst and / or oxide of a transition metal or basic metal hydroxide or carbonate as a promoter further increases the degree of demetallization. .
    In Examples 118-171, experiments were carried out periodically using a 300 ml autoclave.
    The examples use residual petroleum and atmospheric residual petroleum. Properties of residual petroleum products are presented in table. 10 (b).
    In examples 118-135, atmospheric oil residues are used, in examples 136-171, atmospheric oil residues (c) are used. The reaction conditions used in these examples are presented in table. 19. All experiments were performed at 400 s, with the exception of the cases specified in Table. nineteen.
    The experiments in examples 118-123 were carried out at, experiment 150 - at, experiments 151-153, 155, 156 - at, the rest at. Osmium, ruthenium, and rhodium. iridium is introduced in the form OsClj. 3N / 2.0, KiSTS (1-3) H2.0, KHSTs- and. respectively.
    In run 149, water additionally contains 5 g of 1-hexene as an additional source of hydrogen.
    Experimental data are presented in table. 20. Percent recovery of sulfur, vanadium and nickel is obtained from analysis of the combined light and heavy fractions.
    In experiment 126, the combined fractions have an H / C of 1.524, - in experiment 127 - 1.644 in experiment 165 - 1.7.
    The data table. 20 indicate that the cracking and desulfurization in the experiments performed takes place in the absence of a catalyst introduced from an external source, as well as in experiments carried out in the presence of a catalyst. However, the addition of a catalyst from an external source significantly increases the yields of gases and light fractions even after a noticeable decrease in reaction time.
    In addition, the addition of a promoter to the catalytic system causes an increase in both the absolute gas yield, T & and the gas: solid phase yield ratio. The use of a quantity of water sufficient to maintain the water at the edge {0.1 measure / g / ml, i.e. the use of carbon-hydrogen feed and water in such a ratio that the water: hydrocarbon feed weight ratio is relatively high also increases the yield of gas and light fractions and increases the degree of desulfurization compared to the degree of desulfurization obtained at a relatively low weight ratio : hydrocarbon. The introduction of 1-hexane, a donor of 15 g of natum, into the reaction mixture leads to a decrease in the yield of solid product and an increase in the yield of light fractions.
    Sulfur recovered from petroleum residues is found in. products in the form of elemental sulfur, when the density is at least 0.1 g / M.i, i.e. when the weight ratio of hydrocarbon water is relatively jc but low, for example 1: 1, 1: 2 and 1: 3.
    When the water density is less than 0.1 g / mp, i.e. Korita uses a relatively low weight ratio of hydrocarbon: water, part of the sulfur recovered from the hydrocarbon feedstock, is in the products in the form of hydrogen sulfide.
    Examples 172-188 use vacuum oil residues and atmospheric oil residues. The properties of oil residues are presented in Table 35. 10 (b). Examples 172-174 are carried out using vacuum oil residues; examples 175-178 are atmospheric oil residues. The reaction conditions used in these examples are presented in table. 21. All experiments were carried out at. Experimental data are presented in table.
    Catalysts - ruthenium, - osmium, rhodium are introduced as RuCI v (1 3) H. j OzSTsN O and RhCI. ZN O, respectively .97.
    In experiments 178-180, water additionally contains 10 h of ethanol, in experiment 181 - 10 g of 1-Gexane, in experience 20 g of ethanol, in experiment 183 - 30 g of ethanol.
    The data table. 22 indicate that satisfactory desulfurization and demetallization of vacuum and atmospheric petroleum residues is achieved. As a result of the cracking of vacuum oil-bearing residues, a certain amount of g; the elements and light fractions occur, but not to the same extent as in the case of 60 oil-bearing sandy rocks and atmospheric oil residues.
    The cracking of atmospheric oil residues proceeds more easily than the cracking of vacuum oil-bearing residues.
    KING atmospheric petroleum residues in the absence of a catalyst introduced from external sources leads to large yields of solid products. As a result of cracking such a hydrocarbon feed in the presence of a ruthenium catalyst or a rhodium-osmium catalyst introduced from external sources, the yield of light fractions increases. but the yield of the solid product does not decrease.
    By cracking this hydrocarbon feed, flowing in the presence of an iron-manganese or ruthenium-osmium catalyst or in the presence of a hydrogen donor, such as ethanol or 1-hexene, added to water, the yield of solids decreases and the yield of light fractions increases.
    Example 189 illustrates the process of denitrifying anhydrocarbons by this method. 15.7 g of 1-hexene are subjected to processing 91.4 g of water containing 1 ml (0.97 g) of pyrrole in the presence of 0.1 g of a soluble KiSC catalyst (1-3) at a temperature reaction, a reaction pressure of 237 kg / cm and an argon pressure of 45.5 kg / cm for 2 hours. The obtained products contain gases (10.1 l) at normal temperature and pressure, 14.4 g of liquid hydrocarbon products. The gaseous products consist mainly of argon and contain 6.56% of carbon dioxide and 1.13% by weight of methane. The liquid hydrocarbon product contains 888 ppm of nitrogen with 93% nitrogen recovery from the hydrocarbon feedstock. . Examples 190-192 indicate that the catalyst is resistant to nitrogen action. In each of these examples, 12.8 g of 1-hexene is exposed to 90 g of water at a reaction temperature of argon pressure of 45.5 kg / cm in the presence of 2.0 g of silica-dioxide containing 5 wt. ruthenium catalyst for 4 h. The catalyst applied to the substrate is calcined in an oxygen atmosphere for 4 h at 550 ° C. Examples 190, 191 and 192 are carried out at reaction pressures of 245, 246 and 238 kg / cm, respectively. Into the reaction mixture in Examples 191, 192, 1 ml {0.97 g) pyrrole was additionally introduced. Example 192 was carried out under conditions identical to those used in Example 191. In addition to Tort in Example 192, the Catalyst used for conducting the experiments in Example 191 was used etoruously for Example 191. The hexane yields in Examples 190-192 were 16.6,14.0, and 13.9 wt.% Calculated on the feedstock, respectively.
    Examples 193-202 illustrate the semicontinuous process at the 400C straight chain distillate of petroleum sands (properties of which are listed in Table 10) under various conditions. The flowchart used in these examples is shown in FIG. 7. Prior to the start of the experiment, inert spherical alundum beads with a diameter of 0.318 cm or irregularly shaped titanium oxide particles containing 2% by weight of a ruthenium catalyst are poured through the top into a tubular vertical reactor 1, which is 54.6 cm long and has an outer diameter of 2.54 cm and an internal diameter of 0.635 cm. Then the upper part of the reactor is closed and a heating device is installed along its entire length. The tubular reactor has a common
    an effective heated volume of about 23 ml, filled up, the material has a total effective heated volume of about 6 ml. In this way,
    in a tubular reactor, the effective heated free space is about 6 mp. With all valves open except 2 and 3, the system is purged with argon or nitrogen. Then, with valves 4, 5, 6, 7, 8, 9, 2, 3, 9 and valves 10, which are installed on the gas outlet from the system when the required pressure in the system is exceeded, the pressure in the entire system results in a value within 70 140 kg / cm using argon or nitrogen, which enters the system through the valve 11 through line 12. Then the valve 11 is closed. The pressure in the system is adjusted to the required level by opening the valve 2 and pumping water by pump 13 through line 14 to the water tank 15. The water is intended to further compress the gas and further increase the pressure in the system. If a higher volume of water is required to increase the pressure in the system to the required level compared to the volume of the water tank 15, valve 3 is opened via line 16, additional water is pumped into the collector 17. When the pressure in the system reaches the required level, valves 2 and 3 close up.
    The feedstock and water are fed by a pump 18. The pump has two 250-millimeter drums (not shown). Raw materials are loaded into one drum, and water into the other at ambient temperature and atmospheric pressure. Pistons (not shown) inside these drums are manually rotated until the pressure in each drum compares with the pressure in the system. When the pressures in the drums and in the system are equal, the check valves 4 and 5 open, through which the raw materials and water from the drums flow through lines 19 and 20 into the reactor 1. At this time, the valve 21 is closed to prevent flow
    lines 22 between points 23 and 24. Then the RAW and water flows are connected. at point 25, at ambient temperature and required pressure, and along line 26, is directed to the bottom
    tubular reactor 1. The reaction mixture leaves the tubular reactor via line 27 through point 28. Point 28 is located 48 cm from the bottom of the reactor.
    During the temperature increase in the tubular reactor 1 and up to the establishment of a stationary mode, the valves 29 and 30 are closed, the valve 31 is open and the mixture through it through
    Proceeds to storage in the collection 17.
    Once stationary, the valve 31 is closed and the valve 30 is opened for the required period of time to allow the mixture to flow from line 27 through line 30 to storage in the receiver 34 of the finished product 34. Once in the receiver of the finished product for a certain period of time a certain amount of product, valve 30 is closed, and valve 29 is opened to allow the mixture through line 27 and line 35 to be deposited in the receiver of the finished product 36. Then valve 29 is closed.
    The mixture in line 27 is a mixture of gaseous and liquid phases. When the mixture enters the collector 17 and the finished product receiver. 34 and 36, the gaseous and liquid phases are separated and gases are removed from the collector 17 and finished product receivers 34 and 36 through lines 37-39, respectively, and through line 40
    valve 10 is directed to a collection tank (not shown).
    At the end of the experiment, the temperature in the tubular reactor is reduced to ambient temperature, the whole system
    decompressed by opening valve 9 to the atmosphere.
    The diaphragm 41 serves to measure the differential pressure along the length of the tubular reactor.
    The specific gravity of the collected liquid products and the content of nickel, vanadium and iron in them are determined using the X-ray fluorescence method.
    The experimental conditions and characteristics of the products formed in these examples are presented in Table. 23. The hourly volumetric flow rate of a fluid is calculated by dividing the total volumetric flow rate in millilit-i
    per hour of water and hydrocarbon pitak mixture passing through the tubular reactor to the free space of the tubular reactor, i.e. per bMP. The manufacturing process used in Examples 192-202 can be modified to pump the suspension of oil shale particles, oil-bearing sand particles or coal particles into a water-containing tubular reactor. In this case, there are no alundum balls in the reactor, collection 17, receivers of finished products. 34 and 36 can be equipped with a device, such as a diaphragm, designed to separate the spent particles of raw materials from the separated hydrocarbon product; Tubular reactor can be. it is also filled with oil shale particles, oil sands or coal instead of or in addition to the materials used in Examples 193-202. Thus, a continuous or semi-continuous technological process can be used for the extraction process. Except where otherwise indicated, the following experimental procedure is used in each case. Coal feedstock containing water. The liquid and components of the catalytic system, if used, are loaded at ambient temperature into a 300-ml autoclave in which the components of the reaction mixture are mixed. The components of the catalytic system are introduced as solutions in a liquid containing water or as solid particles suspended in a liquid containing water. Except where otherwise indicated, a sufficient amount of water is added in each example so that at temperature, reaction pressure and reaction volume the density of water is at least 0.1 g / ml. The autoclave is flushed with inert argon gas and then closed. Argon is also added to increase the pressure in the reaction system. The temperature in the reaction system is then raised to the desired level, while providing a dense phase containing water. The heating of the autoclave from ambient temperature to 349 ° C takes about 28 minutes. About 6 minutes is required to raise the temperature from 349 to, to raise the temperature from 371 to, it takes about another 6 minutes. Upon reaching the desired final temperature, it was kept constant for the required period of time. During the reaction time, the pressure of the reaction system increases as the reaction proceeds. After a certain reaction time has elapsed at a certain temperature and pressure, the dense water-containing phase is decompressed by rapid stripping of the reactor and the argon, gaseous products, water and oils are removed. Bitumen, solid residue and catalyst, if used, remain in the reactor. The oil is a liquid hydrocarbon fraction boiling at or below the reaction temperature, and bitumen is a liquid hydrocarbon fraction boiling above the reaction temperature, the solid residue is the remaining solid coal. Argon, gaseous products, water and oil are captured in a high-pressure vessel cooled with liquid nitrogen. Argon and gaseous products are removed by heating the vessel to room temperature. Gaseous products are analyzed by mass spectrometry, gas chromatography and infrared spectroscopy. Water and oil are removed from the high pressure vessel using compressed gas and simultaneously heating the vessel. Water and oil are then separated by decantation. The oil is analyzed for its sulfur content by X-ray fluorescence. The bitumen, the solid residue, the catalyst, if used, is washed out of the reactor with chloroform. The solid residue and the catalyst, if used, are then separated from the solution containing bitumen by filtration. Bitumen and solid residue are analyzed for sulfur content. Three carbon samples were used in the experiments. The pieces of coal are crushed and sieved to obtain fractions with different particle sizes. Particle size and moisture content and sulfur in each sample used are presented in table. 24. Sample A is a supra-bituminous coal, Samples B and C are highly volatile fat coals. These samples are stored in an argon atmosphere until they are used. Experiments were carried out in a 300 ml stem. The experimental conditions and the results obtained in these examples are presented in table. 25 and 26. In examples 203-224, RuC 1-3) H20 is used as a catalyst in examples 225-226 - alkali NaOH. In these examples, liquid hydrocarbon products are classified as oil or as bitumen, depending on whether or not it was possible to blow these compounds out of the autoclave when it was decompressed at a given test temperature. Under oil, liquid products are meant that were blown out at the temperature of the experiment, under the bitumens remaining in the autoclave. In examples 207/223, the co-solvent is methyl alcohol, in example 209, biphenyl, in examples 210211 and 224 highly saturated solvent extracted oil, not containing sulfur, containing 4.5 weight of aromatic carbon atoms and 33.7 wt.% Naphthenic hydrocarbons. oils g / ml. In example 212-214, the co-solvent is a highly saturated, hydrotreated white oil containing no sulfur, aromatic carbon atoms and containing 44.3 wt.% naphthenic carbon atoms. Weight of oil 0.8835 g / cm. In Examples 215-217, the co-solvent is a decanted oil, a by-product, extracted by catalytic cracking of cyclones, containing 3.5% by weight and 51% by weight of aromatic carbon atoms and having sp. weight 1.0569 In Example 220, 1.2 g of 85% (by weight) phosphoric acid is added to water additionally. In Example 222, the catalytic system further comprises 0.1 g IrCU- (1-3) H20 as a catalyst and 0.3 g sodium carbonate as a promoter. In Examples 223 and 224, the catalytic system additionally contains 0.3 g of sodium carbonate as a promoter. The weight balance presented in tab. 26, obtained by dividing the sum of the weights of gas, liquid and solid products extracted during the experiment, and the weight of the extracted water, argon and catalyst, if used, by the sum of the weight of coal, water,
    Oil sample
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    22.3 of the solvent, argon, and catalyst, if used, were initially loaded into the autoclave. The composition of the product, presented as a weight percentage without water, was calculated by dividing the weight of this product in grams by the difference between the weight of the coal raw material in grams and its moisture content in grams. The percentage of coal conversion is 1X) 0 minus the weight percentage of the extracted substances. The data presented in table 26, indicate that when using the method there is a significant conversion of both fat and nadbitumnyh coals. In each case, when the sulfur content of the products was determined, substantial desulfurization was observed. The addition of a catalyst in the implementation of the method in Examples 218-226 led to an increase in the formation of oil, fractions relative to gas and bitumen fractions. The data of examples 211, 212 and 214 indicate that the organic cosolvent does not change the amount of extracted solid products. Therefore quantity. solids remaining after processing is a fairly clear measure of the degree of conversion of solid coal to gaseous and liquid products even in the presence of a cosolvent. Typically, the degree of carbon conversion is significantly increased when the co-solvent is a saturated, non-aromatic oil or biphenyl. The various components of the catalytic system do not have the same efficiency. - The predominant choice of these components and their concentration, as well as the choice of other reaction conditions, depends on the nature of the initial carbon-containing raw material. Table
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    权利要求:
    Claims (8)
    [1]
    1. METHOD FOR PRODUCING HYDROCARBON FRACTIONS FROM CARBON-CONTAINING RAW MATERIALS selected from the group including oil shales, oil-bearing sandy rocks, coal, gas oil and residual oil products by contacting the feedstock with water at elevated temperature and pressure, because , in order to increase the yield of the target products, the feedstock is brought into contact with water with a density of 0.1-0.7 g / ml if it is gas oil and residual products, at 374-482 ° C, if they are oil sand and a stone s coal at 315-482®S, or if they are used with oil-bearing | shale, tar sand threshold | <yes, coal, gas oil, and OC p tatochnye oil at temperature. round 315-482 ° C in the presence of an additionally introduced catalyst containing metal carbonates, metal hydroxides and transition metal compounds, and the process is carried out at a pressure of 211-1055 kg / cm ^.
    1,029,830 A
    [2]
    2. The method of pop. 1, characterized in that when using coal as a raw material, water containing an additive of an organic solvent is used at a weight ratio of water to solvent equal to 2.25-17: 1.
    [3]
    3. The method of pop. 2, they are distinguished by the fact that diphenyl, pyridine, and oil fractions are used as an organic solvent.
    [4]
    4. The method according to PP. 1-4 ^ characterized in that the process (Carried out in the presence of a sulfur-resistant catalyst selected from the group consisting of alkali metal carbonate, alkali metal hydroxide, oxide or oxide-forming metal salt of 1UV, UV, UV1V and UPV groups of the Periodic system of elements or combinations thereof .
    [5]
    5. The method according to PP. 1-4, characterized in that the process is carried out in the presence of sulfur and nitrogen resistant: a catalyst is a metal chloride selected from the group consisting of ruthenium, rhodium, iridium, osmium, palladium, nickel, cobalt, platinum, or combinations thereof.
    [6]
    6. The method according to p. 5, characterized in that the process is carried out in the presence of a catalyst containing a promoter selected from the group consisting of alkali metal carbonate, alkali metal hydroxide, metal oxide or oxide-forming salt of 1UV, UV, UV1V, UPV groups of the Periodic Table of the Elements or combinations thereof.
    [7]
    7. The method according to PP. 1-6, with the fact that the process is carried out. wood with a contact time of 0.015 -
    6.0 h
    [8]
    8. The method according to PP. 1-7, which consists in the fact that when using gas oil and residual oil products as a raw material, the process is carried out at a ratio of raw materials: water 1: 1-1: 10, when using oil shale, oil-bearing sandy rocks, coal - at a ratio of raw materials: water 3: 2-1: 10.
    Priority on items 31.05.74 on pp. 1, 4-8 01.07.74 pp, 2.3
    12
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US47490774A| true| 1974-05-31|1974-05-31|
    US05/474,928|US3989618A|1974-05-31|1974-05-31|Process for upgrading a hydrocarbon fraction|
    US05/474,927|US3960706A|1974-05-31|1974-05-31|Process for upgrading a hydrocarbon fraction|
    US05/474,909|US3948755A|1974-05-31|1974-05-31|Process for recovering and upgrading hydrocarbons from oil shale and tar sands|
    US05/474,908|US3948754A|1974-05-31|1974-05-31|Process for recovering and upgrading hydrocarbons from oil shale and tar sands|
    US05/474,913|US3960708A|1974-05-31|1974-05-31|Process for upgrading a hydrocarbon fraction|
    US48458274A| true| 1974-07-01|1974-07-01|
    US05/484,593|US3988238A|1974-07-01|1974-07-01|Process for recovering upgraded products from coal|
    US05/484,594|US3983027A|1974-07-01|1974-07-01|Process for recovering upgraded products from coal|
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