前苏联专利SU910125A3 Process for producing ash-free solid and liquid fuel from coal

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1499332 Destructive hydrogenation GULF OIL CORP 25 June 1974 [4 March 1974] 28160/74 Heading C5E Deashed solid and liquid fuels are made from coal by contacting the coal (10) with hydrogen (40) and an incompletely hydrogenated hydroaromatic solvent (14) to form a slurry (16) in contact with hydrogen, passing the slurry through a preheater (18) that has a ratio of length to diameter of at least 100, so as to inhibit backmixing, for a residence time between 0À01 and 0À25 hours and so that the relative viscosity, which first rises to at least 20, then falls below 10 and finally begins to rise again, has not yet risen the second time beyond 10, to an outlet temperature of 400 to 525‹ C., cooling the slurry by at least 10‹ C., e.g. by adding cool makeup hydrogen at 12, to prevent a further rise in relative viscosity, passing the slurry to a dissolver (24) and holding it there, with mixing, for a time longer than in the preheater, but at a lower temperature between 350‹ C. and 475‹ C., removing the slurry from the dissolver, separating it into a gaseous fraction (30), a liquid fuel product (42) and a deashed solid fuel product (46), and recycling the hydrogen and part of the liquid fuel. A mixture of carbonic oxide and steam may be used in place of hydrogen. The ash precursors in the raw coal act as catalysts; no other catalyst is added.
公开号:SU910125A3
申请号:SU742053471
申请日:1974-08-02
公开日:1982-02-28
发明作者:Рэймонд Пастор Джеральд；Губерт Райт Чарльз
申请人:Галф Ойл Корпорейшн (Фирма)；
IPC主号:

专利说明:

; The conversion of GMS coal to the treatment time in the preheater} in FIG. k dependence of the sulfur content in the ash-free coal on the total residence time in the preheater and at the dissolution stage at different maximum temperatures of the preheater; in fig. 5 shows the dependence of the fraction of organic sulfur removed from the vacuum deposit (de-ashed solid fuel) as a function of the residence time at various temperatures in FIG. 6. dependence of the hydrocarbon gas yield on the output temperature of the preheater at a processing time of 0.035 h; in fig. 7 is a graph of hydrogen consumption, temperature and time of processing
The installation contains a heating tube (heater) 1, located in the furnace 2, the solvent unit 3, the evaporation chamber, the vacuum distillation column 5, the filter 6, the scrubber 7, the conveyor belt 8.
The installation works as follows.
The crushed coal is loaded into the process via line 9 in contact with recycled hydrogen from line 10 and forms a suspension with recycled solvent coming through line 11, the suspension passes through line 12 to the heating tube 1 with a large length to diameter ratio, more than 100, preferably more than 1000 to provide batch flow. The heating pipe 1 is located in the furnace 2, so that in the heating temperature the temperature of the portion of feed slurry r is increased from the inlet temperature to the maximum temperature at the outlet of the preheater.
The heated slurry from the preheater is then passed through line 13, where it is cooled before entering the solvent unit 3 by adding cooling hydrogen through the line. Among other cooling methods, water injection, a heat exchanger, or any other suitable means can be used. The residence time in the solvent unit 3 is substantially longer than the residence time in the preheater 1 due to the fact that the ratio of length to diameter is in solvent. node 3 is significantly less than in heater 1, and causes the opposite
mixing and loss of batch flow. The suspension in the solvent unit 3 is at a uniform temperature, while in the preheater 1 the temperature of the suspension increases from its inlet to the outlet.
The slurry leaving the solvent unit 3 passes through line 15 to the evaporation chamber, from which a lighter overhead flow passes through line 16 to the vacuum distillation column 5, the ash-containing heavy fuel is removed as an evaporation residue through line 17 and passes into the filter 6. The ash from the evaporative residue is removed through line 18, and the ashless sludge passes into the vacuum distillation column 5 through line 19.
Gases, including recycled hydrogen, are removed as an overhead stream from the distillation column 5 through line 20 and either removed from the process through line 21 or passed through line 22 to the scrubber 7 to remove impurities through line 23 and prepare a stream of purified hydrogen for recycling to the next pass through line 10.
The liquid distillate of the process product is removed from the middle zone of the distillation column B through line 2C as the liquid product of the process. Since the process produces a sufficient amount of liquid recovered as a liquid fuel, plus enough liquid to be recirculated in the solvent for the next cycle, part of the liquid product is sent through line 25 for recirculation to line 11 to be used for dissolving carbon in the following cycle.
The vacuum precipitate is removed from the distillation column 5 through line 2b and passes to the moving conveyor belt 8. On the conveyor belt 8, the precipitate is cooled to room temperature, at which time it solidifies. Desalted solid fuel containing so little ash that can be used as intended it is scraped from the conveyor belt 8 by means of an appropriate means 27. As shown in Fig. 1, the material is not removed between the preheater and the solvent stage, and all the material entering into heater, passes through the heater, so
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and through the solvent node, before any product separation occurs. The process produces a deashed solid fuel (dissolved coal, along with possibly a large amount of liquid fuel derived from coal, with an increase in the amount of liquid fuel accompanied by a decrease in the amount of solid fuel. Liquid fuel is a more valuable product, but the production of liquid fuel is limited because it is produced undesired byproducts of hydrocarbons. Although liquid fuel is of greater economic value than de-ashesized solid fuels containing coal Euro hydrogen gases are of less economic interest than de-ashed solid fuel or liquid fuel, and the hydrogen to carbon ratio is higher in them than in solid fuel or in liquid fuel, so their production is unproductive compared to other fuels, but also unproductive from the point of hydrogen production.
Hydrocarbon containing gases are produced primarily by hydrocracking, and since they are undesirable in this process do not use an external catalyst, since the catalysts generally bring carbon-cracking action into the solvation process.
With the solvation of raw coal at a relatively low temperature, the dissolved product contains mainly high molecular weight fuels that are solid at room temperature. Upon subsequent filtration of the solvent mixture with the dissolved coal in order to remove ash and undissolved coal, followed by treatment of the filtrate by vacuum distillation, said boiling solid fuel is recovered in the form of sludge. Desalted vacuum sludge is referred to in the description as vacuum sludge or ashless solid fuel. The vacuum sludge is cooled to room temperature on a conveyor belt and scraped from the belt in the form of lumpy disintegrated fuel containing hydrocarbon.
With the gradual increase in the temperature of the solvation process, vacuum sludge (de-ashes solid fuel) is high.
the molecular polymer is converted into a liquid, hydrocarbon containing fuel with a low molecular weight, chemically similar to the solvent, at 5 ohms in the process, with the same boiling point. The liquid fuel thus obtained is partly recycled as a process solvent and is referred to below as liquid fuel.
About fuel, or as excess solvent. The production of liquid fuel takes place due to the polymerization of solid fuel during various reactions, for example, the removal of heteroatoms from it, including sulfur and oxygen.8 As a result of depolymerization reactions, liquid fuel acquires a slightly higher ratio of hydrogen to carbon than solid fuel and
This, when burned, exhibits a higher heat content. When carrying out this process, it is desirable to convert the entire amount of vacuum sludge (solid fuel) into a product with
5 a boiling point the same as the solvent (liquid fuel), since liquid fuel is more economically valuable than solid fuel from an economic point of view. As the temperature of the solvation continues to increase, the fuel with the boiling point of the solvent converts the increasing amount of vacuum sludge until the temperature reaches
5, at which the conversion of vacuum sludge into liquid fuel occurs only due to the excessive and unproductive formation of relatively hydrogen-rich hydrocarbon by-products under the influence of excessive thermal hydrocracking. The present process gives from 80 to weight. de-solidified fuel to a dry ash-free mass of coal (GMS coal), the rest of the product being mainly liquid fuel.
The aim of the invention is to eliminate thermal hydrocracking, at least to such an extent that excessive production of hydrocarbon gases is avoided, since the formation of gases reduces the yield of the desired neutralized solid fuel.
And liquid fuel.
The goal is achieved by carrying out the process of solvation in two sections. stage, and each stage uses a different temperature. In one embodiment of the invention, not less than 6 wt. hydrocarbon gases based on coal raw material MAF. The performance limit of hydrocarbon gases determines the yield limit for liquid fuels, and therefore also solid fuels. The advantage of the two temperature process is that the high temperature step can be carried out, thereby reducing the sulfur content of the product. Dp sulfur removal requires relatively high temperatures. In addition, high temperatures cause hydrocracking, but the reaction of hydrocracking is more time dependent and, by rapidly reducing process temperatures, a decrease in sulfur content is achieved with a minimum of hydrocracking. The first ctyneHb of the process reactor is a tubular preheater with a relatively short residence time, in which the temperature of the raw coal slurry with solvent as a batch flow gradually rises as it flows through the pipe. The tubular heater has a length to diameter ratio of at least 100 and preferably at least 1UOO. As the temperature increases from a low inlet, temperature To the maximum or output temperature, at which the flow remains only for a short time, a series of basic reactions occur in the current flow. The second stage reactor a is distinguished by a relatively long period of stay in a larger vessel, in which a uniform temperature is maintained throughout all of its volume. One of the important features of the invention is that adjustable forced cooling emanates between the stages npoi, so that the temperature of the second stage is lower than the maximum temperature in the heater. At the same time, the stage works with batch flow without significant reverse mixing, full solvent mixing occurs at a uniform temperature in the reactor at the stage of dissolution. The data presented below show that the process of dissolution of coal gives a high conversion of raw coal to ashless 9 5 8 solid fuel and liquid fuel and the ratio between liquid and solid fuels increases while eliminating the excess production of side hydrocarbon grooves. Below it is shown that these results can be achieved by using a process with different temperatures. The carbon solvent for this process contains liquid hydro-aromatic compounds. The coal is suspended with the solvent and loaded into the first (preheating stage. In the first stage, the hydrogen is transferred from the hydroaromatic compounds of the solvent to the coal material containing hydrocarbons, resulting in coal swelling and 6 hydrocarbons from the Tyulemeters. The maximum temperature limits vary by The first stage is 400-525 C or, preferably. 425-500 C. If this does not manage to properly contain the formation of side hydrocarbon gases, the upper temperature limit should not be 1Tr increase to 70 ° C in order to minimize the formation of gaseous products. The residence time in the first stage is 0.01 hO, 25 hours or, preferably 0.01 to 0.15 h. In the second solvent stage, the solvent compounds combined by hydrogen and converted to their aromatic precursors, by donating hydrogen to coal in the first stage, react with the gaseous gas and reconvert to hydroaromatic compounds for recycling to the first stage. The temperature in the dissolution step is 350, preferably 400-A50 ° C. The residence time in the solvent stage is 0.1-3.0 hours, preferably 0.15-1.0 hours. The temperature in the dissolution stage is lower than the maximum temperature in the heating stage. In order to reduce the flow temperature between the preheater and the solvent, any suitable forced cooling step may be used. For example, fresh hydrogen can be introduced into the process between the heating and solvent stages, or a heat exchanger can be used. The spatial velocity of the fluid in the process (the amount of slurry per hour per volume of the reactor is 0.2-8.00, preferably 0.5 3.0. The ratio of hydrogen to slurry is 3.6-180 standard cubic meters per 100 Preferably, 990 standard cubic meters per 100 liters. The weight ratio of solvent recycled to coal in the feed slurry is 0, preferably 1.0: 1-2.5: 1. Reactions in both stages occur. In contact with hydrogen gas and in both stages, heteroatomic sulfur and oxygen are extracted from the solvated carbon polymer, h It causes the depolymerization and conversion of dissolved carbon polymers into sweet and deoxygenated free radicals with a reduced molecular weight; These free radicals tend to repolymerize at high temperatures, reached at the preheating stage, but at a reduced temperature of the solvent stage, these free radicals manifest There is a tendency to overcome the polymerization due to the introduction of hydrogen into the free radical. In the present process, carbon monoxide can be used with steam together or instead of hydrogen, since carbon monoxide and steam react with each other to form hydrogen. Steam can be obtained from a wet coal feed, or by injecting water. The reaction of hydrogen with a free radical is easier at a relatively lower temperature in the solvent stage than at a higher exit temperature of the preheater. I It is advantageous to get the solvent used at the start of the process from coal. Its composition may vary depending on the properties of the coal from which it is derived. In general, the solvent is a highly aromatic liquid obtained from a previous treatment of the fuel, and usually boils at temperatures in the range of about 150 to 50 ° C. Other common characteristics include a density of about 1.1 and a molar ratio of carbon to hydrogen ranging from about 1.0–0.9 to approx.
1.0-0.3. As the starting solvent in this process, any organic solvent can be used, separated by the viscosity of the pure solvent fed to the process, measured at, t. e, tel ang. Preferably, anthracene or creosote wax may be used as starting solvent with t. kip approximately 220 - 00 ° C. However, the starting solvent is only. a temporary component of the process, because during the process of dissolving the raw coal fraction is an additional solvent which, when added to the starting solvent, gives the total amount of r. The solvent is greater than the amount of starting solvent. Thus, the original solvent gradually loses its composition and approaches the composition of the solvent formed by dissolving and depolymerizing coal in the process. Therefore, at each cycle of the process after the start-up, the solvent should be considered;: as part of the liquid product: the raw coal obtained in the previous extraction. The residence time of the dissolution stage in the heating stage is a crucial parameter. Although the duration of the solvation process varies depending on each type of coal being treated, changes in viscosity as the slurry flows through the preheater tube determines the residence time of the slurry in the heating stage. The viscosity of the feed solution flowing through the preheater increases initially with increasing treatment time in the preheater, after which the viscosity decreases and the solubility of the suspension continues. The viscosity may increase again at the preheater temperature, but the residence time in the preheater ends before the second relatively large viscosity increase is possible. The relative viscosity of the solution obtained in the preheater, which is the ratio of the viscosity of the resulting solution to the viscosity of the solvent supplied to the process, is measured at. -The term relative viscosity is the viscosity at 99 ° C of the solution, 11 The viscosity of the solution when Relative viscosity of the solvent at Relative viscosity can be used as an indicator of the residence time of the solution in the preheater, Los imparting the suspension to solubility occurs during the flow through The preheater, the relative viscosity of the solution, first rises above 20 to the point at which the solution is extremely viscous and has the appearance of a gel. Indeed, when using | low solvency ratios for coal. for example, 0. 5; 1. the suspension goes to gel. After reaching a maximally composite viscosity above 20, it begins to decrease to a minimum, after which it shows a distinct tendency to increase to a higher value. F (soluble); and continues until the relative viscosity increases (following the initial increase in relative viscosity) to a value at least below 10. after which the residence time in the preheater ends with, the solution is cooled and proceeds to a dissolution stage, in which a lower temperature is maintained, with a target | preventing a new increase in relative viscosity to a value greater than 10. Typically, a reduction in relative viscosity allows a value to be less than 5, preferably in the range of 1.5-2. The conditions in the preheater are such that the relative viscosity rises again to a value of more than 10 in the absence of abrupt termination of the output conditions of the preheater, by forcibly lowering the temperature. When the Portion of the hydroaromatic solvent and carbon is first heated in the preheater, the first reaction product is a gel formed at a temperature in the range of 200-300 0. Gel formation is due to a first boost, relative viscosity. . The gel is formed due to the binding of hydroaromatic compounds of the solvent to the hydrocarbon material coal and is manifested in swelling of the coal. Binding is penetration. hydrogen atoms hydroaromatic solvent between the solvent coal as an early stage of the transfer of hydrogen from the solvent to coal. The binding is so strong that, in the gel state, the solvent cannot be removed from the coal by distillation. Further heating of the portion in the preheater causes the arrangement of the gel, indicating the completion of the transfer of hydrogen to produce an ashless solid fuel, liquid fuel and gaseous products and {decrease in relative viscosity. The decrease in relative viscosity in the preheater is also caused by the depolymerization of solvatirovi others. carbon polymers to obtain free radicals from them. Depolymerization is caused by the removal of reTjepo atoms of sulfur and oxygen from containing carbohydrate-coal polymers and the breaking of carbon-carbon bonds by hydrocracking for the purpose of conversion. these ob. Soldered solid fuels into liquid fuels and gases. Depolymerization is accompanied by the release of hydrogen sulfide, where | Carbon dioxide, methane propane, butane and other carbohydrates. At high temperatures in the exit zone of the preheater, the repolymerization of free radicals represents a reaction that favors the hydrogenation of free radical sites, and which is the reason for the latest tendency for the relative viscosity of the preheater to increase to a value above 10. This second increase in relative viscosity is excluded by the invention. The removal of sulfur and oxygen from solvated volatile solubilized solid fuels is caused by the race of these materials due to the thermal break of the bonds, which liberates the molecular fragments of radicals that show a tendency to subsequent polymerization at elevated temperatures. The temperature drop in the stream caused by forced cooling after the preheating stage leads to the prevention of polymer formation. The observed low sulfur content in the semi-liquid fuel that, when combined with one type of coal feed, is about 0.3 weight. in comparison with 0,7 dI ti, the resulting vacuum sludge (solid fuel) indicates that sulfur is distilled from the solid fuel obtained, with low-sulfur smaller molecular fragments in the form of free radicals remaining. The maximum output temperature of the heater should be in the range of 00-525 C. The residence time in the preheater portion of the feed, necessary to achieve the maximum temperature, is approximately 0, 25 hours. With such a combination of temperature and residence time, there is no problem of coke formation, unless it is stopped. flow, t. e. if you do not increase the time spent in excess of the set. . The yield of hydrocarbon gas under these conditions is less than about 6 wt. %, and the yield of excess solvent (liquid fuel) exceeds about 10 or 15 weight. from the GMS coal supplied to the process, this results in about 20 weight. % solid top. liva. Production of large amounts of gases should be eliminated, because it causes a high consumption of hydrogen and requires special equipment. However, the gas output is more than 6 wt. can be allowed if there is. equipment is available that allows gas to be stored and transported. The relatively low content of sulfur in the vacuum sludge (sanitized solid fuel) indicates that the reaction is extremely complete. This also indicates that the resulting vacuum precipitate is chemically free from ash, so that it can be filtered from it. The hydrogen pressure is 35,300 kg / cm, preferably 50,200 kg / cm. At hydrogen pressures of about 70 kg / cm, the solvent hydrogen tends to establish a npviMepHO ratio of 6.1 weight. % If the hydrogen content in the solvent exceeds this level, then there is a tendency to transfer hydro-aromatic hydrogen to dissolved fuel, which increases the yield of liquid fuels having a higher hydrogen content than solid fuels. If the solvent contains less than 6.1 weight. % of hydrogen. THAT, it tends to trap hydrogen from hydrogen gas at a faster rate than the resulting fuel. After it will be. the stable level of hydrogen content in the solvent was roughly rationed; conformational version, apparently, depends on the catalytic effect of FeS, derivative; . from coal ash. With a change in temperature and time, there are some deviations from this basic situation. Higher temperatures lower the content of hydro-aromatic substances in the system, whereas a quick feed can interfere with the achievement of equilibrium values (lack of time). In addition, higher pressures favor faster balancing and tend to increase the hydroaromatic nature of the system. . In the solvent stage, the aromatic compounds that have captured hydrogen in the preheater react with hydrogen to form hydroaromatic compounds again. Hydroaromatic compounds are partially saturated aromatic compounds. The chemical potential in the preheater is too low to completely saturate the aromatics, providing a significant reaction. This is important because, at the same time, the hydroaromatic compound is. not capable of transporting hydrogen, which is not the way. saturated aromatic compounds. Aromatic varieties of solid fuels tend to remain aromatic or hydroaromatic. The present invention is based on using the effect of time in combination with the effect of temperature in the Preheating stage. It is based on the fact that the temperature effect in the preheater stage is a substantially short-term effect, whereas the temperature effect in the solvent phase requires a relatively longer residence time. A short residence time in the preheater is achieved by using an extension tubular reactor with a ratio of length to diameter of at least 100, and preferably at least 1000, so that after reaching the maximum temperature of the preheater, the flow from the preheater is released and the effect of elevated temperature is terminated by forced cooling. Forced cooling can be performed either by hydrogen cooling or by heat exchange. Thereafter, in the dissolution stage, where the temperature is lower, the residence time is increased to a duration longer than the residence time in the preheater. In tab. 1 shows data showing that when using excessively high temperatures a harmful effect occurs in the preheater. . Allowing the maximum temperature of the preheater to or to 500 C gives an increased yield of gases containing carbon to hydrogen, to a level greater than 6 wt. from coal-raw material GMS. The output of the hydrocarbon gas in the amount of 6 wt. based. GMS is a sufficient upper limit for gas production, unless there is special equipment for handling gas. Hydrocarbon gases not only represent a significantly lower economic value than liquid and gas-free solid fuel, but they contain a significantly higher ratio of hydrogen to carbon than any liquid or gas-free solid fuel. Therefore, excessive production of hydrocarbon gases not only means a lower yield of liquid and solid fuels, but also leads to excessive consumption. Hydrogen introduced into the process (due to hydrocracking of high molecular weight fuel, which produces similar hydrocarbon gases. In tab. Figure 1 shows that much better results are obtained when the maximum temperature in the preheater is higher than the temperature in the solvent stage, provided that the maximum temperature of the preheater is less than 75 ° C (for example, lower). Ispol. the knowledge of the temperature of the preheater and the temperature, the temperature in the dissolving stage but . Not A50 C in both stages gives a ratio of excess solvent yield (liquid fuel) to vacuum sludge output (solid fuel), an increase in coal conversion and a decrease in sulfur content in excess solvent plus vacuum sludge and in the most vacuum sludge. Results show significant advantages produced by using a higher temperature at the outlet of the preheater than in the dissolution stage, in comparison with the same temperature at the exit of the preheater and in the dissolution stage, even despite t That is different temperatures gives an overall lowering of the average temperature in the process. The data table. 1 show that even when using the maximum temperature in the heater and a lower temperature in the solvent stage, the ratio of the solvent yield to the yield of vacuum sludge, the percentage of conversion,. total sulfur content in the liquid and vacuum sludge and sulfur content in the vacuum sludge is improved compared to the test, in which it is used: The same TeMnepfaTypa exits at the preheater outlet and at the dissolution stage, but the improvement is achieved due to excessive release of hydrocarbon gas of about 6 weight . % The temperature of the preheater should preferably not be. be above C60-C7 ° C and in the order of 50 or too C before entering the solvent stage. In some cases, it may be more effective to reduce the degree of cooling to at least 10, 15 or less than the maximum output temperature of the preheater. Tab. Figure 1 shows a particularly advantageous temperature difference, because the yield of a liquid product (excess solvent) is greater than the yield of vacuum sludge (solid de-ashes fuel) at IT, the yield of hydrocarbon gas is relatively low. . . Higher temperatures in the solvent phase can be successfully used only in combination with a shorter residence time in the preheater than in the solvent stage. Most of the residence time in the preheater is used to heat the suspension / solvent mixture to the maximum preheat temperature TejTTfl. The reactions occurring in the preheater proceed quickly at the required maximum temperature in combination with a short residence time. On the other hand, reactions occurring in the solvent stage are slower reactions. Therefore, the solvent node acts not only at a lower temperature than the maximum temperature in the preheater, but also for a longer residence time. Although the preheater significantly prevents backmixing, a significant mixing occurs in the solvent node, helping to maintain a uniform temperature throughout solvent site. In the solvent stage, reactions require a lower temperature than the maximum temperature of the preheater. Rehydrogenation of aromatic compounds in a solvent in order to replenish the hydrogen lost by the solvent through a hydrogen preheater in the preheater requires a longer residence time than the time required in the preheater but leads to a temperature lower than the preheater temperature. After the solvent has been hydrogenated in the solvent stage to reconvert the aromatics to the hydroaromatics, it can be recycled. In addition to the formation of hydroaromatic compounds with it, the reaction of removing additional sulfur from the extracted coal that occurs in the preheater also coincides. With respect to Bbico, the heating temperatures are more effective for removing sulfur than low temperatures in the solvent stage. However, it is not possible to remove some sulfur in the short residence time in the preheater. Therefore, the additional sulfur contained in the coal is removed during the extended residence in the solvent stage. The third reaction, occurring in the solvent stage, is a reaction, as a result of which the addition of -. The hydrogen is harnessed to the free radicals formed in both the preheater and the dissolution stage to stop the polymerization of the molecular fragments into a material with a high molecular weight. In tab. 2 shows the results of tests of the heater, carried out at. Some of these experiments were carried out with very Kf: aT time spent in the heater (0.035 h3, and others - with a little more than 91 long periods of stay in the heater. For the shortest residence time, there is a clear loss of liquid solvent (due to the binding of the solvent to the gel). The percentage of coal conversion also decreases. However, with a longer residence time, a pure solvent production takes place and the percentage of coal conversion is significantly higher. Excessive residence time in the preheater is detrimental because repolymerization occurs (which is from the second increase in relative viscosity to a level above 1p), but the insufficient residence time in the preheater is also undesirable at the desired temperature in the preheater, since the process does not satisfy its solvent requirements and there is insufficient conversion of coal. The solvent should be supplied from an external source only at the start of the process, and as soon as the process reaches equilibrium, it satisfies the needs and does not depend on any external sources of solvent. Tab. 3 shows the results of the test T1 carried out with and for a very short residence time in the preheater (0.036 h), during which the net loss of solvent in the Process takes place. The loss is caused by the solubilization of the solvent in a gel with charcoal, from which the solvent does not have enough time, and from which the solvent can be separated by distillation. However, at / t TS C, there is a net loss of solvent in the process when the residence time in the preheater is increased. In addition, if the temperature is raised to 500 ° C, the residence time can be reduced again, obtaining a high racial productivity. in the process. In tab. 4 shows the results of tests performed at a relatively average temperature of the heater A50c. At 50 ° C, lengthening the residence time in the preheater results in the release of hydrocarbon gases above 6 wt. % As the residence time in the preheater increases from about 0.5 to about 1.3 hours at a constant temperature in the preheater, the yield of vacuum sludge (solid fuel) gradually decreases, while the yield of solvent (liquid fuels) gradually increases with an undesirable increase in hydrocarbon gas yield . The hydrogen content in the solvent obtained with a short residence time is lower in comparison with the solvent obtained with a longer residence time at a given temperature, so that the quality of the solvent obtained with a short residence time decreases during the preheating stage. The temperature of the AO heater in combination with a short residence time gives a low yield of hydrocarbon gases. These data illustrate the effect of the residence time in the preheater at the preheater temperature Q C. There is a continuous conversion of vacuum sludge (solid fuel) into solvent (liquid fuel), accompanied by continuous conversion of the product into hydrocarbon gases,. The data table. 3 show that with a high maximum temperature of the preheater 475 and the effect of the residence time tends to increase in comparison with the effect at lower temperatures of the preheater. With a residence time of 0.036 hours, the temperature tends to compensate for the short walking time, so that a pure solvent production takes place in the process and the solvent yield increases When (accompanied by a decrease in the yield of vacuum sludge) by increasing the residence time to 0.130 hours With a residence time of 0.130 hours at 500 ° C, a higher yield of solvent and a lower yield of vacuum precipitate are obtained than at 75 ° C, except that at 500 ° C the yield of hydrocarbon gas is higher. 3 shows a test carried out at a temperature of 450 ° C and at about the same residence time, the solvent yield being lower, and the yield of the vacuum precipitate being higher than at. Moreover, the test at 500 ° C, conducted for 0.130 hours, gives a vacuum precipitate only 0, 8% sulfur, which is the lowest sulfur content in the vacuum precipitation during all tests. A test at 500 ° C and for 0.13 Uh indicates that the amount of vacuum precipitate produced decreases. favor not only of a liquid product, but also in favor of gaseous products. As the level of vacuum precipitation decreases, it can be seen that the conversion to gases occurs under increasing favorable conditions and therefore tends to ultimately limit the degree of conversion of vacuum precipitates into a liquid product. However, if there is equipment for the collection and purification of gaseous products, then a high level of production of hydrocarbon gas can be advantageously used as a commercial fuel, Table 3 shows that at such high temperatures as 75 or. gas production may affect the limitation of the total amount of fuel produced (liquid fuel plus solid fuel). Test 4 (Table 3) shows the highest yield of both liquid and solid fuels (84.6%), and this yield is greater than the output in tests 3 and 5, because in test k there is a relatively low yield of hydrocarbon gases. When comparing tests 3 and 4, it can be seen that the maximum temperature of the preheater is low enough so that a longer residence time (over 0.5 h) is required to ensure significantly higher yields of excess solvent (liquid fuel). Most importantly, at elevated temperatures, the preheater (. Table 3J, the yield of excess solvent is much more sensitive to insignificant changes in the residence time than at 450 C. In order to obtain significant increases in solvent yield, significant increases in processing time are needed. Of all the tests table. 3 and 4, the highest solvent yield and the smallest vacuum precipitate yield a combination at the preheater temperature and residence time in the preheater for 0.130 hours (Table 3). These data show that the solvent output decreases the shorter half time at the residence time and at the preheater temperature one third at approximately the same residence time, but at a lower temperature of the preheater, and more than half at the same processing time and at 50 50 s. It can be seen that there is a significant interdependence between the temperature of the preheater and the processing time in the preheater. The significant difference with the action of the preheater at 500 ° C, when the highest solvent yield is obtained in comparison with the temperature of 450 ° C, is that working at a low temperature does not cnoco6cTByet quickly polymerize free radicals obtained by solvation. In tab. k shows data illustrating the effect on the sulfur content in the product of an extended treatment time in the preheater at a constant temperature of the preheater 450 ° C. The conversion rate reaches a maximum for all tested processing times. However, the sulfur yield decreases with decreasing processing time. Tab. 5 shows the results obtained with a change in the output of the maximum temperature of the preheater, without changing the total time, of the treatment in the preheater. At a constant treatment time of 0.035 hours, the solvent is consumed due to the formation of a gel at low temperatures of the preheater. . Solvent loss decreases with preheater temperature, but even at higher preheater temperatures, the use of extremely low treatment times does not ensure complete gel destruction and freeing of the solvent. The data table. 5 shows that the necessary time must pass to obtain a clear solution exit. a solvent, whereby the solvent process can be maintained itself. The minimum residence time in the preheater should be sufficient to obtain at least a pure solvent yield.
The data table. Figure 5 illustrates the previously explained explanation of the increase in specific viscosity at the beginning of the suspension supply through the preheater in the form of a portion flow. Increasing the specific viscosity in the stream to
Tab. 6 shows the results of tests carried out at maximum temperatures in the preheater and at variable residence time in the preheater. At preheater temperature C and at mV over 20, it is due to the formation of a gel between the grinding or raw coal fed to the process raising the temperature of the carbon slurry with the solvent in the preheater. This gel is formed due to the start of the addition of hydrogen from the hydroaromatic solvent to the coal and arises due to the binding of the solvent to the coal during the start of the transfer of hydrogen. This binding is somewhat strong that the solvent in the gel cannot be separated from the gel by distillation at this stage of the reaction. As the temperature continues along the length of the preheater to about hydrogen transfer from the solvent to the coal, it further proceeds to such an extent that the gel is destroyed. The high viscosity hydrocarbon polymer dissolves from the coal and enters the solution along with the solvent, causing a decrease in the relative viscosity of the solvent containing polymer, to a value below 20. With further flow into the preheater zone with a higher temperature, sulfur and oxygen heteroatoms are removed from the dissolved polymer, causing depolymeris ation and the polymer forming free radicals, which occurs due to a further decrease in the viscosity of the solution. The relative viscosity drops to a value below 10 or 5 or 2. Free depolymerized coal radicals repolymerize under conditions of elevated temperature, reaching the preheater exit level, unless the residence time in the preheater has expired and the temperature of the solution is not forcedly lowered. At this time, the preheater stream is removed from the preheater, the hydrogenone is cooled {or otherwise and passed to a lower temperature solvent stage before the free radicals can repolymerize to such an extent that the relative viscosity rises again to a value greater than 10. 0.035 there is a clear loss of solvent. The preheater can give a clean yield of solvent either by extending the residence time at the preheater temperature or by increasing the final preheater temperature by up to without extending the residence time, which illustrates the replaceability of the preheat temperature and the residence time in the heater. FIG. Figure 2 shows that very high yields are obtained at a temperature at least at a constant low processing time. FIG. J shows the percentage of coal conversion depending on the residence time in the preheater; FIG. 3 is based on the data obtained with ,, shows that the maximum conversion is achieved (above 80 or S5) very quickly in the preheater and the length of time spent in the preheater has a much greater effect on the conversion as a whole little effect. Therefore, at 50 ° C in the preheater after being in it for about 0.05 to 0.1 hours, the residence time in the preheater, as a factor in the conversion process, ceases. FIG. shows the sulfur content in the ash coal depending on the total presence in the preheater and in the dissolution stage at different maximum temperatures of the preheater; FIG. 4 shows that the residence time has a greater effect on the level of sulfur content in a vacuum sludge at a high temperature than at a low temperature. If a significant amount of sulfur needs to be removed without the use of relatively high temperatures, then the low temperature process must be accompanied by an extended residence time. Therefore, a solvent is used at a relatively low temperature and a relatively long residence time to achieve sulfur removal in excess of possible sizes in a single preheater operating at a high temperature, at which a long residence time is unacceptable due to the onset of hydrocracking. Thus, a two-temperature process gives a product with a lower sulfur content than during operation of the preheater and solvent stage at the same temperature, even it has the same temperature above any temperature of the two-temperature process. It is important that the use of a higher average, but equal temperature in the preheater and in the solvent stage does not provide advantages in terms of sulfur removal, but better results are obtained at different temperatures, when the relatively lower temperature in the solvent stage is compensated by a longer residence time. FIG. Figure 5 shows the limited sulfur fraction removed from the vacuum sludge (coarse solid fuel), depending on the residence time at different temperatures. A high level of sulfur removal does not depend much on the residence time at a higher temperature, then the residence time becomes important to remove sulfur at a high temperature. . FIG. Figure 5 again illustrates the basis for using the relatively low-temperature solvent stage in combination with an extended residence time when interacting with the relatively high-temperature one. heater with a relatively short residence time. FIG. 6 illustrates the relationship between the release of hydrocarbon gas and the preheater exit temperature over a residence time of 0.035 hours, and shows that the hydrocracking to gases quickly rises as the temperature rises above and especially above 50 ° C. The present invention allows a high conversion without excessive hydrocracking due to high temperature only for a short duration (in the preheater stage) followed by a relatively low temperature with a longer residence time (dissolve stage). Thus, high conversion is achieved without a high yield of hydrocarbon gases. The release of hydrocarbon gases means product waste and excessive consumption of hydrogen, unless equipment is used to treat gases.
2591
Fig. -7 illustrates the effect of temperature and residence time on the flow rate of hydrogen and shows that with a short residence time the temperature does not affect the flow rate of hydrogen, HCI with a longer residence time (above 0 or 0.5 hours), the temperature affects on hydrogen consumption. Low hydrogen consumption contributes to
012526
either a short residence time or low temperature. Therefore, in the stand-up | gm process, a relatively short residence time is used in a heater with 5 relatively high temperatures, while a relatively longer residence time is used at
relatively low temperature in the solvent stage.
Table 1
27
28
910125
LRODOLEM table. t
T vilits 3
31
32
910125 Continuation of the table.
Excess solvent (fuel distillate)
Vacuum Sludge (Solid Fuel)
h
Undissolved organic material
Total:
Conversion, weight.
Vacuum sediment, weight.%; Hydrogen pressure, kg / cm Temperature heaters, C 200 300 Fluid velocity, h 28.09 28.09 Gas velocity, m 2978 2978
6.00 11.73
I, 74 16.98 18.97
69.78 65.0264.3661.3258.83
11.10 10.6210.6010,129.6
100.08 102.18101,24101,20108.17
88.90 89,3889.4089.88 90.36 707070 350400450 27.9628.3628.36 2978.9CH7ZO
33
Excess solvent (fuel oil)
Vacuum Sludge (Solid Fuel)
Undiluted organic material
Extract, weight Conversion, wt.%
H
910125 Continuation of table.5
-134.95 129 5b-38.47 167.60 187.58 65.57
67.08 40.21 71.06 27.02 92.19 94.14 32.97 59.79 28.94
Table 6

权利要求:
Claims (1)
[1]
1. Pilot plant to upgrade coal. Chem. Eng, 1973, 80, ff 6, pL2l 4.
W
t
80
S §
70 60
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I
tO 30
I
I iff
I
i
"
0 100 wo 300 tOO SOO 600
I JeMrmpamy / ja. in ao in revsupa / z with
Riga.1
ut.Z
I
0.0O.S1.0
Put, 3
1.f
f-ui.t
1.0 0.9 0.8 0.7
0.6 O.S Л40 .3 O.i 0.1
"ST
L)
Z.O
1.B
1.6
five
I I
1 "a
S 1.2.
I
3o
§ 1.0
I;
"
"3
"four
0.8 ",
e
ro t
A9
I
I
j ..
t
O.Z
0.0
0 100 iOO 300 S 500 600 100 Tempersipura in the heat / pele with
rZf
l.f .b
0.0
After the time of the day
t50 ° C
1.0
1.5rig .7

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引用文献:

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WO2011136695A1|2010-04-27|2011-11-03|Stepanenko Yury Mikhailovich|Plant for producing a composite fuel based on industrial and organic waste|US3341447A|1965-01-18|1967-09-12|Willard C Bull|Solvation process for carbonaceous fuels|

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JPS5444002B2|1975-05-21|1979-12-24|

US4057484A|1975-12-15|1977-11-08|John Michael Malek|Process for hydroliquefying coal or like carbonaceous solid materials|

AU506174B2|1976-05-28|1979-12-13|Kobe Steel Limited|Coal liquefaction|

US4201655A|1976-12-17|1980-05-06|Continental Oil Company|Process for making metallurgical coke|

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DE2909333C2|1979-03-09|1985-10-17|Linde Ag, 6200 Wiesbaden|Process for the biological purification of waste water|

GB2053955B|1979-07-17|1983-01-26|Coal Industry Patents Ltd|Coal extraction|

US4421630A|1981-10-05|1983-12-20|International Coal Refining Company|Process for coal liquefaction in staged dissolvers|

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US4534847A|1984-01-16|1985-08-13|International Coal Refining Company|Process for producing low-sulfur boiler fuel by hydrotreatment of solvent deashed SRC|

CA1238287A|1984-08-04|1988-06-21|Werner Dohler|Process for the production of reformer feed andheating oil or diesel oil from coal|

DE3527129A1|1985-07-29|1987-01-29|Inst Vysokikh Temperatur Akade|Process for making liquid products from coal|

JP4660608B2|2009-06-22|2011-03-30|株式会社神戸製鋼所|Carbon material manufacturing method|

JP2013136692A|2011-12-28|2013-07-11|Kobe Steel Ltd|Production method for ashless coal|

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法律状态:

优先权:

申请号 | 申请日 | 专利标题

US446971A|US3892654A|1974-03-04|1974-03-04|Dual temperature coal solvation process|

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