• 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:
    A process for the production of a mixture of methanol and higher alcohols of "fuel grade" from CO and H2. To reduce the water content in the mixture coming from the synthesis reactor of the synthesis of the alcohols, the reaction product is cooled down and is fed to a secondary reactor wherein the conversion reaction CO+H2O-><-CO2+H2 is carried on in conditions near to equilibrium. The further product of reaction is cooled in a more thorough manner so as to obtain a liquid phase constituted by the "fuel grade" mixture of alcohols and a gaseous phase which after the discharge of the inert substances and after elimination of the CO2 is recycled to the synthesis reactor. In the secondary conversion reactor operation is carried out with a temperature comprised between 150 DEG C. and 250 DEG C., at a pressure equal to that of the synthesis reactor and in the presence of a copper catalyst.
    公开号:SU1428187A3
    申请号:SU813280252
    申请日:1981-05-11
    公开日:1988-09-30
    发明作者:Ди Пиетро Рафаэле；Паггини Альберто；Лагана Винченцо
    申请人:Снампрогетти С.П.А. (Фирма)；
    IPC主号:
    专利说明:

    j; ib to
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    00
    The invention relates to aliphatic alcohols, namely, to a method for producing a mixture of methanol and alcohols, which can be used as a fuel in pure form or in a mixture with gasoline.
    The aim of the invention is to increase the yield and quality of the target product.
    The goal is achieved by the interaction of a gas mixture containing 41.4 - 43.5% by volume of CO and 53-58.1% by volume. Ng, at 360-415 ° C, pressure of 100-260 atm in the presence of a catalyst, composition, wt.%: ZnO 59.80-72.18; 25.4- 37.7; CgO 1.45-4.0, or Catalyst, composition, wt.%: ZnO 65.8; CrjOj 28.3; CuO 1.7; KjO 0.9; MnOj 3,3, with subsequent cooling of the mixture and its interaction at 1b5-200 ° C and pressure ytm in the presence of a catalyst composition, wt.%: ZnO 25.9-31.4; CrgOa 36.7-49.9; CuO 18.7- 38.4, or catalyst composition, wt.%: ZnO 53.7; CuO 32.8 - AlgOa 13.5, followed by cooling the reaction mixture. Separating the liquid mixture of methanol and Cg-C /) - alcohols and recycling the gas mixture to the first stage.
    The drawing presents a flow chart for implementing the method.
    Synthesis 1 and recirculated 3 gases are compressed to operating pressure and fed through line 2 to reactor 7, the reaction product leaves the synthesis reactor through line 4 and after cooling in recuperator 15, is sent to conversion reactor 16, where the water content in it is significantly reduced.
    The reacted gas is discharged from the conversion reactor through line 5, first sent to heat recuperator 14, then to condenser 11 and then to separator 12, from the base of which fuel mixture of alcohol is removed through line 10, and gas nozzle 6 is removed which is partially removed through part 8, a-partly through part 9 is sent to the CO 13 absorption section and then returned to the synthesis reactor 7.
    Example 1. In accordance with the process flow, a gas mixture consisting of the following is fed into the synthesis reactor along with the recycle gas:
    CO CO2
    H,
    N
    nm Uch.% 6055.9 41.40 0.27 Minor amount
    8509.2 58.10 55.72 0.38
    NJ, 5.14; SI4 0.85 vol.% CHjOH traces
    Synthesis reaction The catalyst has the following composition, wt.%: ZnO 72,18; CrjOj 25.98; 2.08. The volume of catalyst 10 m, temperature 410 pressure 260 atm.
    The composition at point 2 in the drawing is as follows:
    WITH 46,96% vol. 33190.4 norms
    m 3 / h SOg 0.0 vol.% 30 cubic meters
    / h
    Hg 46,485% vol. 33190.4
    3636.1 601.1
    tracks / total 70,648.82 cubic meters
    ghSV (7064.9 hours / h gas.a flow rate)
    Conversion reaction. Use 20 m of catalyst, which has a composition, wt.%: ZnO 31.4, CrjO 49.9 copper oxide 18.7, ghSV 3073.4 / h, pressure 260 atm, temperature 200 ° C,
    After the synthesis reaction in the reactor 7 of thermal recovery in 15 and the conversion reaction in reactor 16, a product is obtained consisting of: vol.% From 27599.2 44.84 COa 1031.7 1.68
    40.80 5.92 0.97 5.10 0.1 1 0.19
     234.4 0.38 HgO 7.7 0.01 This reaction product, after pre-cooling, is sent to a separator 12, from the base of which an alcohol-grade fuel mixture of the following composition is removed through line 10:
    kg / h vol.% CHjOH, 4508 78.5 CjHffOH 138 2.4
    SzN, OH 3205,57
    C4HsOH 77313.4
    HjO60.1
     P p and m e p 2 (comparative). c This example shows how important the selection of the operation mode of a conversion reactor is. If the temperature of this reactor were equal to the temperature of the synthesis reactor, the operator would receive 10 alcohol mixture containing 7.600 ppm of water, i.e. too much for this mixture to be fuel grade.
    For simplicity, a thermal recuperator 15 is excluded from the above -15 technological scheme, and the synthesis reaction is carried out in one reactor 7 with a conversion reaction.
    Into the synthesis reactor, together with an as-20 rotating gas, a gas mixture of the composition is supplied:
    nm / h vol.%
    CO 6008.2 41.14
    C0 "0.27
     773.8 13.37 HiO 44.5 0.76 ExampleZ. This example shows that to obtain an alcohol mixture with a higher content of higher alcohols, it is still possible to obtain a mixture of fuel grade in accordance with the invention.
    A recirculation gas is fed to the synthesis reactor together with a gas mixture of the composition:
    nm / h
    WITH 6341.2 WITH 0.27
    Ht 8223.9 NI 55.72 CH4 18.3 For the synthesis-use
    vol.% 43.32 Insignificant amount of 56.17 0.38 0.12 12 m of a catalyst of the following composition, wt.%: ZnO 70.6; CrjOa 25.4; 4.0, pressure 200 atm, temperature, ghSV Non-significant, 25 5887 / H. For the conversion reaction, the amount is used. 58.45 0.38 0.12
    Not 8556.9 nz 55.72
    CH 18.3 0.12 A synthesis catalyst is analogous to Example 1, with the same temperature, pressure and gas hourly flow rate (ghSV), where the conversion catalyst is an industrial SK-12 catalyst made of a light fraction (iron oxide with oxide). chromium).
    Temperature, pressure 260 atm, volume 20 m, ghSV 3073.4 / 4.
    The reaction product of the following composition is recovered from the reactor:
     % CO 27646.9 44.98 COg 984 1.61 Ng 24965.4 40.62 Nj 3636.1 5.92 CH 601.1 0.97 CH, OH 3159.82 5.14 CjHjOH 67.24 0 , 1 CsH-, OH 119.5 0.19 234.38 0.38 HjO 55.38 0.09 which, after cooling, gives an alcohol mixture of the following composition:
    kg / h% vol. СНзОН 4508 77.98. CgHjOH 138 2.38 320 5.51
     773.8 13.37 HiO 44.5 0.76 ExampleZ. This example shows that to obtain an alcohol mixture with a higher content of higher alcohols, it is still possible to obtain a mixture of fuel grade in accordance with the invention.
    A recirculation gas is fed to the synthesis reactor together with a gas mixture of the composition:
    nm / h
    6341.2 0.27
    8223.9 55.72 18.3 synthesis-use
    vol.% 43.32 Insignificant amount 56.17 0.38 0.12 12 m catalys 20 m of catalyst, composition, wt%: ZnO 53.7; copper oxide 32.8; AlzOa 13.5. Temperature, pressure 200 atm, ghSV 3073.4 / h.
    After the synthesis reaction in the reactor 7, thermal recovery in 15 and conversion reaction in the reactor 16 receive the product composition:
    they / cho. X
    СО27313,944.45
    COi13172,16
    Na25298,441.15
    Nj, 3636,15,92
    SND 601,10,97
    CHjGH2702,84,39
    CjHs-OH 3 30,21
    SzN, OH20,80,33
    OH250.40.40
    HjO100.02
    In condensed form, this product produces an alcoholic mixture of the following:
    kg / h
    3855.5
    275.5
    551
    8.03
    826.6
    4. a)
    CHjGH
    CiHffOH
    NgO
    C4H90N
    Prim
    e p
    vol.% 69.88 4.99 9.99 0.16 14.98 Reactor synthesis,
    Catalyst composition, wt.%: ZnO 65.8; 28.3; CCA 1.7; KjO 0.9; MnOj 3.3, pressure 100 at, temperature 375-415 ° С, volume velocity 25 m / / 7200 h.
    and hydrogen at elevated temperature and pressure in the presence of a catalyst containing an alkali metal compound, characterized in that, in order to increase the yield and quality of the target product, a gas mixture containing 41.4 - 43.5 vol. CO and 53.0 -58.1% by volume Hj.,
    51428187
    b) Conversion reactor. The composition of the catalyst, wt.%: ZnO 24.9; CreOs 36.7; CuO 38.4, pressure 100 at, temperature 165-1b8 C, volume velocity of 20 h.
    The compositions of the initial flow of reagents, intermediate and final are given in Table. one.
    Primvr5, a) IteaKTop synthesis. 10 is subjected to interaction at 360 - Catalyst composition, wt.%: ZnO 59.8 ;. 415 ° C and 100-260 atm in the presence of CtgOj 37.7; 1.45, the pressure of the catalyst composition, wt.%: ZnO 150 at, temperature 360-410 s, volume 59.80-72.18; 25.4-37.7; KgO is the rate of 13 m / 10500 h, 1.45-4.0 or catalyst composition,
    b) Conversion reactor. The composition of kata-15 wt.%: ZnO 65.8; CrH2 = 28.3; CuO 1.7; ; lysator, wt.%: ZnO 28.6; 0.9 and MnOj 3.3, the resulting reaction mixture, consisting of methanol, C2-C4 alcohols, water and unreacted gases, is cooled, and 40, 7; CuO 30.7, pressure 150 at, temperature 195-198 s, bulk velocity 20 MV6800 h.
    The compositions of the initial reagent fluxes are subject to interaction at comrades, the fluxes after the synthesis reactor are 165–200 ° C and 100–260 atm in the presence and conversion, and the desired product is given in Table. 2
    The proposed method allows to increase the yield of fuel grade alcohols with their high quality: low water content (less than 2000 ppm).
    25
    VII catalyst composition, wt.%: ZnO 25.9-31.4; 36.7-49.9; CuO 18.7- 38.4 or catalyst composition, wt.%: ZnO 53.7; CuO 32.8; AlgOj 13.5. followed by cooling the reaction mixture consisting of methanol of Cr-C4 alcohols, unreacted COg gases and a small amount of water.
    权利要求:
    Claims (1)
    [1]
    The invention claims the separation of a liquid mixture of methanol and C-alcohols of fuel grade and recycling a gas mixture consisting mainly of CO, He and COa, after removing COg from it. to the first stage
    The method of obtaining a mixture of methanol and Cr-C / (fuel-grade alcohols based on the interaction of carbon monoxide and hydrogen at elevated temperature and pressure in the presence of a catalyst containing an alkali metal compound, so that gas mixture containing 41.4 - 43.5 vol. CO and 53.0-58.1% by volume Hj.,
    subjected to interaction at 360 - 415 ° C and 100-260 atm in the presence of a catalyst composition, wt.%: ZnO 59.80-72.18; 25.4-37.7; KgO 1.45-4.0 or catalyst composition,
    Total Tampvr1Tura,
    with
    Avleiun, ata
    18061.4 40 (h l
    100
    .R
    i; "387.7 100.0 166043.4 (00.0 166073.4 100.0 166073.4 100.0 5800.00 100.0
    375 (pairs) 100
    415 (pao)
    100
    165 (steam)
    too
    168 (par)
    100
    40 (liquid)
    S
    Table 1
    168 (par)
    100
    40 (liquid)
    S
    table 2
    类似技术:
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    同族专利:
    公开号 | 公开日
    FR2482583A1|1981-11-20|
    DE3119290A1|1982-03-18|
    FR2482583B1|1985-04-26|
    YU98481A|1983-02-28|
    IT8022116D0|1980-05-16|
    CU21282A3|1985-12-16|
    GB2076015A|1981-11-25|
    DK151381A|1981-11-17|
    AU549850B2|1986-02-20|
    NO154170B|1986-04-21|
    NL8102403A|1981-12-16|
    BR8102809A|1982-02-02|
    BE888794A|1981-11-16|
    GR75227B|1984-07-13|
    GB2076015B|1984-06-13|
    EG15530A|1986-12-30|
    CH648341A5|1985-03-15|
    FI74270B|1987-09-30|
    IE810736L|1981-11-16|
    NO154170C|1986-07-30|
    PL128472B1|1984-01-31|
    ES8203954A1|1982-04-01|
    JPH0232311B2|1990-07-19|
    AU7053981A|1981-11-19|
    IN155655B|1985-02-16|
    IE51147B1|1986-10-15|
    CS224612B2|1984-01-16|
    FI74270C|1988-01-11|
    PL230665A1|1981-12-23|
    ES502751A0|1982-04-01|
    CA1159257A|1983-12-27|
    PH16335A|1983-09-05|
    NZ196719A|1984-03-16|
    FI811516L|1981-11-17|
    TR20776A|1982-07-01|
    US4481012A|1984-11-06|
    DE3119290C2|1984-04-12|
    RO82969A|1984-01-14|
    JPS5710689A|1982-01-20|
    LU83367A1|1982-01-20|
    NO811643L|1981-11-17|
    IT1140947B|1986-10-10|
    SE8103072L|1981-11-17|
    ZA813275B|1982-05-26|
    SE451141B|1987-09-07|
    RO82969B|1984-01-30|
    DD158912A5|1983-02-09|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    BE342014A|
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    US4762858A|1985-09-16|1988-08-09|The Dow Chemical Company|Syngas conversion to oxygenates by reduced yttrium/lanthanide/actinide-modified catalyst|
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    IT1223404B|1987-12-04|1990-09-19|Eniricerche Spa|DIESEL FUEL COMPOSITION|
    ES2090854T3|1992-02-04|1996-10-16|Air Prod & Chem|PROCEDURE TO PRODUCE METHANOL IN LIQUID PHASE WITH RICH IN CO.|
    IT1276931B1|1995-10-13|1997-11-03|Snam Progetti|PROCEDURE FOR PRODUCING MIXTURES OF METHANOL AND HIGHER ALCOHOLS|
    DE69831261D1|1997-10-28|2005-09-22|Univ Kansa Ct For Res Inc|FUEL MIXTURE FOR COMPRESSION SPARKERS WITH LIGHT SYNTHETIC RAW AND MIXED COMPONENTS|
    FR2894251B1|2005-12-05|2008-01-04|Air Liquide|METHANOL SYNTHESIS METHOD FOR RECYCLING RESIDUAL GAS|
    US20080260631A1|2007-04-18|2008-10-23|H2Gen Innovations, Inc.|Hydrogen production process|
    US20090018371A1|2007-07-09|2009-01-15|Range Fuels, Inc.|Methods and apparatus for producing alcohols from syngas|
    PL2173694T3|2007-07-09|2017-06-30|Albemarle Corporation|Methods for producing alcohols from syngas|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT22116/80A|IT1140947B|1980-05-16|1980-05-16|PROCESS FOR THE PRODUCTION OF A MIXTURE OF METHANOL AND HIGHER ALCOHOL "FUEL DEGREE"|
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