• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    In the liquefaction of a sub-bituminous and/or lignitic coal, prior to the liquefaction, the coal is soaked at a temperature of from 550 DEG to 750 DEG F and a pressure of from 30 to 300 psig for a time sufficient to remove at least 10% of the organic oxygen present in the coal to thereby reduce the hydrogen requirements of the liquefaction. The liquefaction is effected with a pasting solvent derived from the sub-bituminous and/or lignitic coal having a 5 volume percent distillation temperature of at least 550 DEG F and containing at least 25 weight percent of material boiling above 800 DEG F. The use of such a pasting solvent provides for improved dispersion of the coal particles during the liquefaction.
    公开号:SU1099847A3
    申请号:SU762367257
    申请日:1976-06-04
    公开日:1984-06-23
    发明作者:Чон-Юан Че Морган；Джозеф Снелл Джордж
    申请人:Дзе Ламмас Компани (Фирма)；
    IPC主号:
    专利说明:

    T
    .
    HMMI invention relates to the processes of obtaining liquid products from coal, and more specifically to the process of hydrogenation of brown coal.  A method of producing liquid hydrocarbons from brown coal is known, which includes pre-treating the carbon with a hydrocarbon solvent boiling. at 287-426 ° C, at 260DOO ° C and a pressure of 2.1-21 kgf / cm to remove more than 10% of bound oxygen and subsequent hydrogenation at, 315-482 ° C and a pressure of 35-280 kgf / cm 1.  The disadvantage of this method is the separation of coal and solvent in the process of hydrogenation, which leads to a decrease in the yield of liquid target products.  The aim of the invention is to increase the yield of the desired products by preventing the separation of coal and solvent.  This goal is achieved by the fact that according to the method of producing liquid hydrocarbons from brown coal, which includes pretreatment of carbon with a hydrocarbon solvent at 260-400 ° C and a pressure of 2.1-21 kgf / cm to remove more than 10% of bound oxygen and subsequent hydrogenation at 315-482 C and a pressure of 35-280 kgf / cm, use a solvent, the contents of more than 25 wt. % fraction boiling at a temperature above 427 C.  The coal to be treated during the hydrogenation process is partially deoxygenated or decarboxylated by heat treatment.  During the treatment, carbon dioxide, water, and small amounts of carbon monoxide are released, which is the main product (s).  Large amounts of organic oxygenated compounds can also be formed, & also a small amount of light hydrocarbon gases (C | -C).  The treatment of the coal before the hydrogenation is carried out under the condition that at least 10% of the organic oxygen contained in the coal is from.  it was removed, and in the general case the content of organic oxygen in coal should be reduced by 15-60%.  Thermal treatment is carried out at a temperature not lower than 250 ° C, usually at a temperature of about 285-400 ° C, and a pressure below 21 atm, usually at a pressure of about 2.1-21 atm.  The heat treatment is carried out for a period of time sufficient to achieve the desired removal of oxygen, this time being 0. , 05-2 hours  It should be noted that although hydrogenation is carried out in a particular type of paste-forming solvent, sub-bituminous and / or lignite coal can be deoxygenated in paste-forming solvents different from those used in the subsequent hydrogenation step.  Pretreatment of brown coal with the implementation of its deoxygenation reduces the gross demand for hydrogen during hydrogenation.  Brown coals have an oxygen content of about 15-30 wt. % (in terms of hot mass) in comparison with bituminous coal, which in general have an oxygen content of 4-12 weight. % (based on the combustible mass).  Consequently, due to deoxygenation and brown coal, the need for hydrogen is significantly reduced during the subsequent hydrogenation.  The hydrogenation of brown coal is carried out using a local paste-making solvent, t. e.  paste-forming solvent originating from brown coal, when the content in the paste-forming solvent is at least 25 weight. % of components boiling above 427 C, preferably 3570 wt. % of components boiling above 427 C.  The pasting solvent has about 5 vol. % of the components having a distillation temperature of about 287 ° C, although lower boiling components may be included in the pasting solvent, t. e.  The paste-forming solvent may include components boiling below 287 ° C, provided that the paste-forming solvent comprises 25 wt. % of components, ccd shchx upper 427 C.  The given temperature values are corrected for 1 atm.  Use of paste-forming solvent of local origin.  having components boiling above A27 ° C in an amount of 25 wt. % for hydrogenation of brown coal, ensures that the coal is in a dispersed state, whereas the use of a paste-forming solvent of local origin, which does not have similar heavier components, leads to a loss of coal dispersion, resulting in coal heating in the reactor and reducing the yield of the target products.  The hydrogenation of brown coal is carried out at 315-426 ° C, preferably 343-454 s, and a pressure of approximately 35-281 atm.  The hydrogenation is generally carried out in the presence of a suitable hydrogenation catalyst, which is typically an oxide and / or sulfide of a metal of groups 65 and / or 8 deposited on a suitable carrier, such as alumina or silica alumina.  Preferred catalysts are molybdate, cobalt, molybdate, nickel, and nickel-wolfram sulfide.  The catalyst can be made in the form of extrudates, tablets, spheres, or randomly shaped particles and can have arbitrary sizes of similar particles, with a preliminary interval of particle sizes ranging from 0.42 to 4.76 mm.  Contacting can be carried out using one of the known methods, including adding a catalyst in the form of a powder, using a fixed bed of a catalyst, a fluidized bed of a catalyst, a fluidized bed, and the like. P.  The preferred method is to use an upward spreading layer.  Hydrogenation can be carried out in one or more reactors, and it is preferable to use a design with a series connection of two or three reactors.  The drawing shows a block diagram illustrating the proposed method.  Crushed, partially dried (moisture 3-15%) brown coal, along line 1 is introduced into the coal suspension zone 2, where the coal is suspended in a paste-forming solvent, injected along line 3.  Spreading. the solvent of local origin contains at least 25 wt. % of components boiling at 425 C.  The suspension of coal in the paste-forming solvent is carried out at 65-230 ° C and a pressure of 0-3.5 ati to obtain a coal suspension in the paste-forming solvent containing 25-45 wt. % ang.  During the suspension operation, a certain amount of water vapor may be introduced, which are removed from the suspension zone by means of a ventilation system.  The coal suspension in the paste-forming solvent is removed from zone 2 of the suspension (pending over line 4 and fed to heat treatment zone 5, where the coal suspension is heat treated to ensure coal deoxygenation, and the deoxygenation products are removed from the treatment area.  The heat treatment zone operates under conditions that provide at least 10% removal, and in general, 15-60% removal of compounds with organic oxygen present in the coal.  Partially deoxyge1-carbonate paste is removed from the treatment zone 5 through line 6 and fed to the hydrogenation zone 7 along with the hydrogen-containing gas entering through line 8.  The hydrogen-containing gas and coal paste can be pre-mixed before entering hydrogenation zone 7.  The hydrogenation zone contains a catalyst and operates under conditions that ensure the hydrogenation of brown coal.  The hydrogenation zone is designed as a reactor with an upwardly expanding layer, with two or three such reactors being connected in series.  It is possible to use other types of reactors in the hydrogenation zone.  The gaseous products are withdrawn from the hydrogenation zone through line 9, and the hydrogenation product of the coal is removed via line 10.  In some cases, part of the hydrogenation product is recycled through line 11, although in most cases such recirculation is not required.  The gross hydrogenation product of coal through line 12 is introduced into the distillation zone 13 to extract lighter components from it.  Zone 13 operates to carry out dyntillation with the separation of materials that reach people at temperatures approximately up to the final boiling point of the desalter liquid promoter, which is used at the subsequent desoldering stage.  The components are more volatile than the boiling ones, at 287-315 C, are removed from zone 13 through line 14, and these products form part of the gross, hydrogenation product of coal l.  The residual product is removed from zone 13 through line 15 and part of it is recycled to suspension zone 2 and / or zone 5 of treatment through line 16, recycling is not performed until the final product contains more than 15 wt. % solids.  The residual product through line 17 enters the mixing zone 18, where the product is mixed with the desalting promoter liquid supplied through line 19.  The liquid promoter should have a characteristic coefficient (K) of approximately 9.75, e, preferably 11.0.  The liquid promoter, which is used to enhance and ensure the separation of insoluble material from the product, hydrogenation of coal, is characterized by a 5% (by volume) content of components, the distillation temperature of which is 121 ° C, and 95% (by volume) content components whose distillation temperature is 176-400 ° C5 and the liquid promoter contains 5 vol. % of components distilling at, and more preferably 204 C.  The temperature of distillation 95 about. % of components below.  The most preferred promoter liquid has a distillation temperature of 5 vol. % of components is 218 ° C, and 95% by volume. % - distillation temperature not higher than 260 C.  The liquid promoter is preferably used in amounts that provide the weight ratio liquid-promoter liquefaction product of the order of O51, 0.  A mixture of the product of hydrogenation. the coal and the promoter liquid, which is passed from the mixing zone along the line 20, goes to the zone 21 of the clearing, where C11 is free from the ashes of pro, the product is separated from the product containing the coal ash.  Desalting zone 21 contains one or several gravity settling tanks with sedimentation under the force of gravity at 204–315 ° C.  The overflow product, free from insoluble material, is withdrawn from the desalinization zone 21 through line 22 and enters the separation zone 23 for. extracting a promoter fluid therefrom.  This liquid is withdrawn from the separation zone 23 via line 24 and mixed, if necessary, with the additional promoter liquid entering via line 25, and introduced into the mixing zone through line 19.  The remaining overflow product divides into two streams, one of the streams is used in line 3 as a paste-forming solvent for the hydrogenation process.  A portion of the pasting solvent can be introduced into zone 5 of the term treatment along line 26.  The rest of the product, not used as a paste-forming solvent, is recovered as gross product via line 27.  Ash enriched sludge product is withdrawn from desalination zone 21 via line 28 and introduced into compartment zone 29 to extract promoter fluid from it. This fluid is withdrawn from compartment zone 29 along line 30 and fed into mixing zone 18.  The remaining ash enriched product is withdrawn from the separation zone 29 through a line.  31 for further processing, for example, the enriched soot stream may undergo coke formation and / or gasification.  Example 1  In a 2 liter beaker at 93 ° C, a coal slurry consisting of 429 g of brown coal is compiled, the analysis of which is given in Table.  1, and 1000 g treated with hydrogenation with brown coal tar.  The prepared mixture is loaded into a nitrogen-flushed 2-liter electrically-heated bomb equipped with a back pressure regulator.  The bomb is closed, the back pressure is set at about 10.5 atm on the controller, and hydrogen is supplied to the vapor zone of the bomb at a flow rate of 0.057 cc / m / h.  Incubating gases from the bomb are cooled and fed to a water cooled separator.  The non-condensable gas from the separator is fed to an integrating flow meter and collected in a rubber gas ball.  The liquid contents of the bomb after its closure are heated to 315 ° C for 15 minutes and held for 20 minutes at 315 seconds.  By the end of this period, the laps read the readings of the integrating flow meter and the gas ball was disconnected with its subsequent blockage.  Dp of the contents of the gas ball is carried out automatic gas chromatographic analysis.  The total amount of carbon dioxide (COO) released with the exhaust gas is calculated on the basis of the preceding gas chromatographic analysis and the total molar amount of waste gas is determined using an integrating flow meter.  About 26% of the organic oxygen present in the coal load is released as carbon dioxide (C02).  Example 2  Example 1 is repeated using a load of a 2-liter bomb consisting of 0 g of lignite and 1000 g of hydroprocessed at 287 ° C angular tar, used in example 1.  Essentially no carbon dioxide is found in the composite waste gas.  Example 3  Coal paste containing 30 wt. % brown coal and 70 wt. % paste-forming solvent, prepared according to example 1 and then placed at 87 ° C in a steam jacket equipped with a stirred feed tank.  The original paste-forming solvent is extracted from hydrotreated lignite tar simulating a solvent of local origin.  This coal paste is fed to the heating coil through a proportional pump, where it is mixed with hydrogen-rich gas under pressure.  The temperature of the mixture of coal paste - hydrogen-rich gas is increased to 287 C.  This mixture of non-ferferon is fed to the catalytic riser of a hydro-hydrogenation plant. Below are the operating conditions of the reactor. The product leaving the reactor is collected in a high-pressure separator / receiver tank with a hot water jacket in which the gas and liquid phases are separated from each other. .  The gas is continuously ventilated from the high pressure receiver separator through a pressure control valve.  When the liquid content of the separator / receiver at high pressure takes about 75-80% of the available volume of the separator / receiver reservoir, the product from the reactor is fed to a similar separator / receiver reservoir at high pressure, pre-adjusted to high pressure with hydrogen-enriched gas to working pressure.  The contents of the first separator / receiver are poured into a liquid product receiver operating at low pressure and having a steam jacket, and this receiver operates at atmospheric pressure.  The liquid product from the resulting low pressure product is transferred to a stirred storage tank having a steam jacket.  The sequence of operations is repeated and thus achieve a continuous mode of operation of the reactor.  The continuous experiment based on brown coal is stopped after 48 hours of operation.  A representative compound sample solution of the liquid product is removed from the stirred storage tank and the volumetric amounts of the product solution are determined along with the temperature of the storage tank.  For this representative liquid solution, the ash content (ASTM-482), the content of quinoline insoluble residue (ASTM-2318) and the specific gravity (ASTM-287) are determined at several temperatures.  From the previous analysis and the weight of the compound solution of the liquid product, it was found that about 83 + 1% (brown coal) fed to the hydrogenation reactor was converted into a product soluble in quinopene, which can be a measure of the degree of hydrogenation.  Over the entire 48-hour operating period, a pressure drop of the reactor was observed in the range of 1.4-1.75 atm.  Example 4, Example 3 is repeated using a slightly lighter paste-forming solvent.  This paste-forming solvent (hydrotreated brown coal tar for modeling) is of local origin.  The conditions of the process are as follows (Example 3, however, a different solvent was used.  After 15 minutes after the commencement of the supply of the coal paste, the pressure drop in the reactor quickly rose from a fairly normal level of 1.401, 75 atm to 21 atm.  A heavy creosote oil, obtained from bituminous coal and stored in a reservoir, is fed into the system and the charcoal paste is stopped.  The hydrogenation reactor is subjected to such washing to those. until the pressure drop in the reactor is restored to a value of 1.40-1.75 ata.  The cream with creosote oil is then interrupted and the reactor is again started to be fed with coal paste, applied to it.  After about 15 minutes. After the secondary injection of the coal paste, the pressure drop across the reactor quickly jumped again to a value above 21 AT.  The system hyd1) coal ogenization at this moment is disabled.  After pressure drop, cooling and flushing with nitrogen, the bottom shell of the reactor is opened and the lower part of the catalyst bed is visually examined.  Regions containing numerous accumulated brown coal particles are clearly visible.  COAL PARTICLES were literally undispersed, precipitated from the paste-forming solvent in the lower part of the catalyst bed, which sharply reduces the permeability of the layer.  Summary analytical data for crushed dried brown coal.  .  Approximate analysis Moisture content, wt. % 6.02 Content of volatile matter, wt. % (DM) 51.48 Ash, wt. % (DM - on a dry basis) 0.86 Bond carbon, wt. % (DM) 47.66 Final Anapiz (taken as a basis) Water, weight L6.02 Ash, weight. % 0.81 Carbon content, wt. % 63.07 Hydrogen content, wt. % (minus water hydrogen) 3.96 N content, wt. % 0.51 Sulfur content, weight. % 0.24 Content of organic bound oxygen, wt. % (by difference) 25,39 Calorific value (dry matter) Maximum calorific value (MW), kcal / kg6100 Summary analytical data for the forming solvent (1) used in Example 3.  Specific weight of the fraction boiling at 59 ° С (measured at 15.6 С), 0269 Specific weight of the fraction 109 ° С / 15, бс1.0224 Ash content, weight. % Sulfur content, weight. % Carbon Content, wt. % 85.86 Content, hydrogen, weight. % 9.35 Nitrogen, wt. % 0.49 Content of components insoluble in benzolb, weight. % 1.5 In the table.  1 shows a vacuum dislocation analysis of the paste-forming solvent (1).  Parameters of the catalytic process used by rimers 2 and 4.  Catalyst Freshly prepared cobalt molybdate on alumina carrier Catalysis form - Spheres with a torus size, mm 2.0-2.38 Charcoal content, weight. % 30.0 Type of contact- Reactor with recovery expansion layer Volume intensity of hourly liquid flow (1 hr / volume of catalyst feed), Working pressure, pressure Gas flow rate to the reactor, lb-mol, gallon of liquid feed Content hydrogen in the make-up gas, mol. % Temp. Atour at the reactor inlet, C 287-315 1099847 and Q 5 20 Pa 25 25 Khogi and 12 Temperature at the reactor inlet, C 415-421 Summary analytical data for the formative solvent (II) used in Example 4.  Specific weight, 107 ° С / 15.6 ° С, g / cm 0.9951 Specific weight, 49 ° / 15.6 ° С, g / cm Ash content, weight. % 0.01 Sulfur content, weight. % 0.37 Carbon content, wt. % 86,24 Hydrogen content, wt. % 9.65 N content, wt. % 0.48 Vacuum-distillation analysis of the forming solvent (II) is given in Table.  2  The present invention makes it possible to use a paste-forming solvent of local origin, which makes it easy to disperse the coal in this solvent to increase the yield of the target products.  Table 1
    0.0
    3.29 8.22 10.41 20.07 26.76 34.47 44.05 53.40 56.65
    220.5
    267
    287.8
    315.6
    326
    354
    371
    383
    403
    418
    426.7
    ABOUT
    2.80 8.73 18.11 29.98 44.12 54.48 64.13 73.78 79.38
    table 2
    234 234 287 315
    354 371 404 410 417 426
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING LIQUID HYDROCARBONS FROM BROWN COAL, including pretreatment of coal with a hydrocarbon solvent at 260-400 ° C and pressure of 2.121 kgf / cm ^ to remove more than 10% of bound oxygen and subsequent hydrogenation at 315-482 ° C and pressure of 35-280 kgf / cm ^, characterized in that, in order to increase the yield of the target products by preventing the separation of coal and solvent, use a solvent containing more
    25 wt.% Fraction boiling at temperatures above 427 ° C.
    >
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    同族专利:
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    RU2460757C1|2008-10-09|2012-09-10|Синфьюэлс Чайна Текнолоджи Ко., Лтд.|Method and equipment for multi-stage liquefying of carbon-containing solid fuel|US2106973A|1931-04-13|1938-02-01|Standard Ig Co|Hydrogenation of high oxygen coal|
    US3540995A|1968-11-14|1970-11-17|Us Interior|H-coal process:slurry oil system|
    US3607719A|1969-11-13|1971-09-21|Hydrocarbon Research Inc|Low-pressure hydrogenation of coal|US4391699A|1976-12-27|1983-07-05|Chevron Research Company|Coal liquefaction process|
    US4330389A|1976-12-27|1982-05-18|Chevron Research Company|Coal liquefaction process|
    US4354920A|1976-12-27|1982-10-19|Chevron Research Company|Coal liquefaction process|
    US4148709A|1977-10-27|1979-04-10|The Lummus Company|Hydroliquefaction of sub-bituminous and lignitic coals to heavy pitch|
    US4177134A|1978-03-20|1979-12-04|Kerr-Mcgee Corporation|Separation technique in a coal deashing process|
    US4326853A|1978-09-13|1982-04-27|The Lummus Company|Coke production from liquid derived from sub-bituminous and/or lignitic coal|
    US4470900A|1978-10-31|1984-09-11|Hri, Inc.|Solids precipitation and polymerization of asphaltenes in coal-derived liquids|
    US4316793A|1979-12-21|1982-02-23|The Lummus Company|Hydroliquefaction of coal|
    US4316792A|1979-12-21|1982-02-23|The Lummus Company|Hydroliquefaction of coal|
    ZA822056B|1981-08-05|1983-02-23|Lummus Co|Coal liquefaction|
    US4415442A|1981-09-24|1983-11-15|Kerr-Mcgee Corporation|Process for the separation of entrained organic fluids from gaseous streams in a coal deashing system|
    US4435269A|1982-04-30|1984-03-06|Phillips Petroleum Company|Conversion of lignite to higher quality fuels|
    AU547073B2|1982-11-09|1985-10-03|New Energy Development Organisation|Method of liquefying coal using an iron based catalyst|
    US4596650A|1984-03-16|1986-06-24|Lummus Crest, Inc.|Liquefaction of sub-bituminous coal|
    US4545890A|1984-04-30|1985-10-08|Lummus Crest, Inc.|Coal liquefaction and hydrogenation|
    US4617105A|1985-09-26|1986-10-14|Air Products And Chemicals, Inc.|Coal liquefaction process using pretreatment with a binary solvent mixture|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US05/584,627|US4028221A|1975-06-06|1975-06-06|Liquefaction of sub-bituminous and lignitic coal|
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