• 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:
    oisture- and ash-free coking coal is micronized and admixed with a recycle oil, whereafter it is rapidly hydrogenated and one portion of the residue of the fractional distillation of the hydrogenation product is sent to hydrotreating, together with hydrogen. Conventional catalysts can be used both for the hydrogenation and the hydrotreating. A gaseous fraction, consisting of water vapour, hydrogen sulphide, ammonia and Cl-C4 hydrocarbon is obtained along with gasoline. Gasoil can be obtained together with gasoline.
    公开号:SU1299517A3
    申请号:SU843752791
    申请日:1984-06-07
    公开日:1987-03-23
    发明作者:Пецци Джианкарло；Карвани Луиджи；Валентини Доменико；Дзанинелли Мичеле
    申请人:Эни-Энте Национале Идрокарбури (Фирма)；
    IPC主号:
    专利说明:

    12
    left fraction, and atmospheric gas oil containing zodorod donor substances used as a solvent. Vacuum gas oil, derived from hydrotreatment products, is hydrocracked in the presence of a pre-sulphurized catalyst containing nickel and molybdenum oxides. Hydrocracking is carried out in two reactors, in the first one, preferably at 350 ° C, and in the second, at 400 ° C with a hydrogen flow rate of 1700 m / m. The hydrocracking products are divided into a vapor-gas stream and octaTOK hydrocracking. The hydrocracking residue is recycled to
    one
    The invention relates to methods for liquefying coal by hydrogenation processes to produce liquid products and can be used in the petrochemical and coal chemical industries.
    The purpose of the invention is to increase the efficiency of the process due to the flexible adjustment of the yield of the target fractions — middle distillates with low hydrogen consumption at the hydrogenation stages.
    The drawing shows a scheme that implements the proposed method.
    The pre-washed coal through line 1, coming from the mine, is fed to the pretreatment stage 2, where the ash content in the coal is reduced to the lowest possible value using well-known gravimetric methods (heavy liquids, cyclones, vibrating screens, vibration tables and similar devices). The ash-rich byproduct of line 3 is directed either to the gas production stage for hydrogen production or to other stages to produce useful process products. Pretreated coal from the low ash content line 4 is mixed with a hydrogen donor supplied through line 5 The mixture of coal and solvent in line 6 is
    17
    hydrocracking stage. Part of it can be used as a solvent. The vapor-gas streams at the stages of coal dissolution and hydrocracking in a mixture with a light stream, separated from the hydrotreatment products, are subjected to fractionation with separation of the target products — gasoline and gas oil oil. As a result of carrying out the above process, 20.44-20.72 wt.% Gaseous products, 17.87-18.5 wt.% Gasoline and 41.46-44.68 wt.% Gas oil and 23.9-24.0 are obtained. % of residue for gas production. 2 hp f-ly, 1 ill.
    go to stage 7 of dissolution where the liquefaction is carried out. The reaction product through line 8 is fed to a fractionation system 9, consisting of high and low pressure separators, where atmospheric evaporation takes place, resulting in the separation of a light stream 10 containing gas, liquefied petroleum gas, gasoline and atmospheric gas oil, and a heavy stream 11 containing gold-containing atmospheric residues and non-reacting coal.
    Stream 11 is divided into two streams 12 and 13. Stream 13 is fed to hydroprocessing stage 14, while stream I2 is part of the recycling solvent supplied via line 5.
    The heavy stream from the dissolution stage 13 is directed to the hydrotreatment stage after a corresponding displacement with hydrogen. The reactor (or reactors) is a slurry-type reactor with a catalyst suspended inside the effluent. The product from the hydrotreatment stage through line 15 is directed to a fractionation system 16 containing high and low pressure separation units, where recycled hydrogen and light stream 17 containing gas, liquefied oil pelvis, gasoline and atmospheric gas oil are released during atmospheric evaporation.
    3129
    The bottom stream 18 contains atmospheric distillation residues. Stream 17 is supplied to fractionation unit 19, where stream 20 containing atmospheric gas oil is separated, with a boiling range corresponding to the highest content of hydrogen donor substances and light stream 21 containing gas, liquefied petroleum gas, gasoline and atmospheric gas oil is separated. . Stream 20 is the lightest component of the recycled solvent 5. Stream 18 is divided into streams 22 and 23. Stream 22 is a component of recycling solvent 5. Stream 23 is fed to vacuum fractionation system 24, where bottom stream 25 is separated, which contains large amounts ash and unreacted ugd. This stream is divided into two streams 26 and 27. Stream 26 is characterized by the same ash content that is in the
    treated coal
    SRI 4, and such a stream is fed to the gas production unit to produce hydrogen, as a result of which the accumulation of ash in the recyclable solvent is prevented.
    Stream 27 may be a component of the recycled solvent 5, but this is not necessary.
    Stream 28, separated from the top of the vacuum fractionation system, mainly contains ashless vacuum gas oil. This stream, after mixing with stream 29, containing unreacted substance, and with hydrogen is fed through line 30 to hydrocracking stage 31 in order to optimize the rate of production of intermediate distillates.
    .
    The reaction product from the hydrocracking step through line 32 is fed to the fractionation system 33, consisting of high and low pressure separators, and is separated into atmospheric evaporation into stream 34 containing the reaction products and stream 35 containing unreacted substance.
    Stream 34 and streams 10 and 21 form stream 36, which is fed to the final stage of the fractionation of the products of the liquefaction process (not-shown), where it is separated to separate the products of the process, such as liquefaction.
    951
    5 f5
    25
    thirty
    35
    40
    50

    -. 74
    oil gas, gasoline, atmospheric gas oil, etc.
    Unreacted substance through line 35 is partially recycled through line 37 to the hydrocracking stage, and partially recycled through line 38 as a component of recycled solvent.
    Line 39 is the hydrogen inlet from an external source.
    Example 1. Use Illinois coal No. 6 as the starting product, which has the following elemental composition (on dry coal), wt.%:
    Carbon69,53
    Hydrogen, 71
    Oxygen11,02
    Nitrogen1,47
    Sulfur2,93
    Ash10.34
    The coal is subjected to a gravimetric type pretreatment stage in order to reduce its ash content to a value of 3% by weight. The yield of such coal is 61.5 May. %
    The treated coal is milled to a granulometric composition of 70-150 microns and mixed with a recycling solvent consisting of middle distillate (204-372 0) obtained at the hydrotreatment stage 2011. 1 wt.%, The bottom stream from the stage of atmospheric fractionation of the product (372 ° C ), obtained from the dissolution stage 12-26.7 wt.%, the bottom stream from the stage of atmospheric fractionation of the product. (C72), obtained from the hydrotreatment stage 2262 .2% by weight.
    Streams 27 and 38 are not used. The weight ratio of solvent to carbon is 1.8: 1. The mixture is fed to the dissolution reactor, in which the following process conditions are maintained: a partial hydrogen pressure of 150 kg / cm, a flow rate of recycling hydrogen 1500 solvent / coal mixture, a temperature of 440 ° C, a contact time of 6 minutes.
    Coal conversion is
    90.3% by weight. The bottom stream resulting from the atmospheric fractionation of the product coming from the dissolving stage is divided into streams 12 and 13 with a mass ratio of 19.5: 80.5. Stream 12 is
    flow recycle boot
    is part of the recycling solvent.
    Stream 3, together with the hydrogen, is fed to the hydrotreatment stage 14. The concentration of ash in the feed is 6.7% by weight. The operating conditions of the reactor are maintained at the following values: hydrogen pressure 150 kg / cm, temperature 410 ° C, volumetric velocity (measured for a flow of Z72 sec) 0.4 h volumetric velocity of ruling hydrogen 1700
    An industrial type catalyst (Shell-S-324) containing nickel and molybdenum oxides in the sulfonated form on an alumina support is used.
    The loading conversion measured for a stream of 372 ° C was 28.8% by weight. In the process of atmospheric fractionation of the reaction product, a fraction with bp is obtained. 204-372 ° C (stream 20), which is partially recycled to the dissolution reactor. The pubic flux from the atmospheric fractionation stage 18 is divided into two streams 22 and 23 in a ratio of 77.5:: 22.5. Stream 22 is recycled to the dissolution reactor, and stream 23 is fed to vacuum fractionation 24.
    The bottom stream 25 after vacuum fractionation, containing 12.5 wt.% Ash, is completely fed to the gas production unit 26. The distillate stream after vacuum distillation is 8.79 wt.% With respect to the mass of coal fed to the dissolution stage, It is fed to the hydrocracking stage, where this part is completely transformed.
    The following reaction conditions are maintained at the hydrocracking stage:
    ) 2nd reactor actor
     ,
    120
    350
    0.5
    120
    400
    0.5
    1700
    1700
    five
    0
    five
    0
    five
    0
    five
    0
    five
    In the first hydrocracking reactor, an industrial catalyst (Cyanamid HDN-30) containing nickel and molybdenum oxides on alumina is used: in the second reactor, a silica catalyst (She11-S-354) containing oxides of nickel and tungsten on silica and alumina is used. Both catalysts are pre-precipitated before use.
    The conversion is 61.0% by weight based on the weight of the charge.
    The balance of the process is presented in the following vi, cent, wt.%: Coal (dry) supplied to the dissolution stage 100 Hydrogen 4.27 Total 104.27 Reaction products, wt%: Gas (HgO,
    NH,
    s; -c,)
    (WITH ),
    20.72 17.87
    Petrol
    204 ° C
    Atmospheric gas burn (204372 ° С) 41.68
    Rest to node
    production
    gas (26) 24.00
    Example 2. The same coal, previously worked in the same manner as in Example I, is mixed with a recycling solvent containing, in wt.%: A middle distillate 204-372 C, obtained from the hydrotreatment stage 20-12.5; bottom flow after atmospheric fractionation of the product obtained by the dissolution stage 12-35.0; bottom flow after atmospheric fractionation of the product obtained from the hydrotreatment stage 22-35.0; bottom flow after vacuum fractionation of the product obtained from the hydrotreatment step 27-17.5.
    Stream 38 is not used. The weight ratio of solvent to carbon is 1.8: 1.
    Under the same process conditions as in Example 1, a dissolution step is carried out with a conversion of 90.1% by weight. The bottom stream 1 I after the atmospheric fractionation is divided into two streams 12 and 13 in a 26/74 mass ratio. Stream 12 is part of the recycling solvent. Stream 13, containing wt.%, Ash, is treated in a staged hydrotreatment under conditions that are identical to example 1.
    The flow conversion is 25.3 wt.%. After atmospheric fractionation, a fraction of the reaction product is obtained with a boiling range of 204-372 ° C (stream 20), which
    partially recycle to the reactor
    dissolving. The bottom stream obtained after atmospheric fractionation 18 is divided into two streams.
    22 and 23 regarding 46:54.

    Stream 22 recycle to the reactor
    dissolve, and stream 23 is fed to flavor fractionation.
    The bottom stream 25 after vacuum fractionation is divided into two streams 26 and 27 at a 43:57 mass ratio. Stream 26 is fed to the gas receiving unit, and stream 27 is the majority of the recycling solvent.
    A vacuum distillate containing 19.19% by weight of the mass of coal fed to the dissolution stage was sent to the hydrocracking stage. The process is carried out under the conditions that in example 1 Conversion is 59.9% by weight.
    The overall balance of the process is as follows, wt.%:
    Coal supplied to the node
    dissolving 100.0 Hydrogen4.31
    Overall 104,31
    Products.reactions, wt.%: Gas (H, p, H, S,. NHj, C, -C) 20.44 Gasoline (C,
    204 ° C) 18.51
    Atmospheric gas oil (20437GS) .41,46
    Residue to gas production unit (26) 23.90
    权利要求:
    Claims (3)
    [1]
    1. A method of liquefying coal by degassing it, then mixing it with a hydrogen donor solvent in a mass ratio of 1: 1.8, liquefying at 440 ° C, separating the liquefaction products with release of a vapor-gas stream containing gas
    0
    with
    -
    0
    five
    0
    five
    0
    various products, gasoline and gas oil fractions and residue containing ash and unreacted coal, catalytic hydroprocessing of the residue at a temperature of 410 C, pressure 150 atm. , flow rate 0.4 h, separation of hydrotreatment products into a vapor-gas stream containing gaseous products, gasoline and gas oil fractions, and residue, separation of a gasoil fraction from the residue, separation of a vapor-gas hydroprocessing stream into a light stream containing gas products of gasoline and gasoil fractions, and to the solvent fraction, supply of hydrotreatment gas oils to catalytic hydrocracking, carried out at 350-400 ° C, 120 atm pressure, flow rate of 0.5 h, the separation of hydrocracking products with combined-cycle flow and hydrocracking residue, combining the combined-cycle vapor flow stages of liquefaction and hydrocracking with a light stream, separated from hydroprocessing products, and feeding them to the separation with separation of the target fractions, which is different in order to increase the efficiency of the process, liquefaction carried out in a hydrogen environment at a pressure of 150 atm., the flow rate of hydrogen supply is 1500 mixture of coal and solvent, contact time is 6 minutes, the residue is liquefied into two streams, the first stream is fed as a solvent to mixed e with deashed coal, the second stream is fed n hydroprocessing, which is carried out at a volumetric flow rate of hydrogen of 1700, the hydroprocessing residue is divided into two streams, the first stream is fed as a solvent for mixing with deashed coal, the second stream is subjected to vacuum distillation with vacuum gas oil and the ash residue, which is fed to the gasification, and hydrocracking are carried out in two reactors at a flow rate of hydrogen supply of 1,700 m / m, followed by recycling of the hydrocracking residue per g idrocracking.
    [2]
    2. The method according to claim 1, characterized in that a portion of the ash residue of vacuum distillation is
    hydroprocessing agent is recirculated as a solvent to the mixing step with coal ash,
    B
    Editor N.Rogulich
    Compiled by E. Gorlov
    TehredN.Morgental Proofreader S.Shekmar
    Order 906/64 Circulation 464 Subscription
    VNIIPI USSR State Committee
    for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab., 4/5
    Production and printing company, Uzhgorod, Projecto st., 4
    129951710
    [3]
    3. The method according to claim 1, characterized by the fact that the hydrocracking in the first reactor is carried out at,. and in the second - at.
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    同族专利:
    公开号 | 公开日
    DE3481314D1|1990-03-15|
    AU565291B2|1987-09-10|
    IT1163480B|1987-04-08|
    EP0128620A2|1984-12-19|
    US4595488A|1986-06-17|
    PL248118A1|1985-03-26|
    ZA844279B|1985-01-30|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3488279A|1967-05-29|1970-01-06|Exxon Research Engineering Co|Two-stage conversion of coal to liquid hydrocarbons|
    US4113602A|1976-06-08|1978-09-12|Exxon Research & Engineering Co.|Integrated process for the production of hydrocarbons from coal or the like in which fines from gasifier are coked with heavy hydrocarbon oil|
    US4075079A|1976-06-09|1978-02-21|Exxon Research & Engineering Co.|Process for the production of hydrocarbons from coal|
    US4048054A|1976-07-23|1977-09-13|Exxon Research And Engineering Company|Liquefaction of coal|
    US4045328A|1976-07-23|1977-08-30|Exxon Research And Engineering Company|Production of hydrogenated coal liquids|
    US4085031A|1976-08-11|1978-04-18|Exxon Research & Engineering Co.|Coal liquefaction with subsequent bottoms pyrolysis|
    US4189371A|1976-08-20|1980-02-19|Exxon Research & Engineering Co.|Multiple-stage hydrogen-donor coal liquefaction process|
    US4060478A|1976-09-30|1977-11-29|Exxon Research And Engineering Company|Coal liquefaction bottoms conversion by coking and gasification|
    US4210518A|1977-01-24|1980-07-01|Exxon Research & Engineering Co.|Hydrogen-donor coal liquefaction process|
    US4125452A|1977-06-10|1978-11-14|Exxon Research & Engineering Co.|Integrated coal liquefaction process|
    US4132627A|1977-12-06|1979-01-02|Leas Arnold M|Integrated coal conversion process|
    US4222844A|1978-05-08|1980-09-16|Exxon Research & Engineering Co.|Use of once-through treat gas to remove the heat of reaction in solvent hydrogenation processes|
    US4338182A|1978-10-13|1982-07-06|Exxon Research & Engineering Co.|Multiple-stage hydrogen-donor coal liquefaction|
    US4227991A|1978-12-15|1980-10-14|Gulf Oil Corporation|Coal liquefaction process with a plurality of feed coals|
    US4410414A|1980-01-18|1983-10-18|Hybrid Energy Systems, Inc.|Method for hydroconversion of solid carbonaceous materials|
    US4297200A|1980-01-18|1981-10-27|Briley Patrick B|Method for hydroconversion of solid carbonaceous materials|
    DE3244251A1|1981-12-07|1983-06-09|HRI, Inc., 08648 Lawrenceville, N.J.|METHOD FOR CARBOHYDRATION USING A THERMAL COUNTERFLOW REACTION ZONE|JPH07108984B2|1985-04-01|1995-11-22|三菱化学株式会社|Hydrocracking method for heavy coal liquefaction|
    US8123934B2|2008-06-18|2012-02-28|Chevron U.S.A., Inc.|System and method for pretreatment of solid carbonaceous material|
    US20110120915A1|2009-11-24|2011-05-26|Chevron U.S.A. Inc.|Hydrogenation of solid carbonaceous materials using mixed catalysts|
    US20110120914A1|2009-11-24|2011-05-26|Chevron U.S.A. Inc.|Hydrogenation of solid carbonaceous materials using mixed catalysts|
    US20110120916A1|2009-11-24|2011-05-26|Chevron U.S.A. Inc.|Hydrogenation of solid carbonaceous materials using mixed catalysts|
    US20110120917A1|2009-11-24|2011-05-26|Chevron U.S.A. Inc.|Hydrogenation of solid carbonaceous materials using mixed catalysts|
    WO2014116272A1|2013-01-25|2014-07-31|H R D Corporation|System and process for coal liquefaction|
    CN103408083B|2013-07-31|2014-07-23|张卫东|Method for processing ammonia water remaining in coke oven through vacuum flash evaporation method|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT21513/83A|IT1163480B|1983-06-08|1983-06-08|STAGE PROCEDURE FOR DIRECT CHARCOAL LIQUEFATION|
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