• 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 device for the cryogenic separation of a synthesis gas comprises a heat exchanger (5) in which the synthesis gas is cooled, a washing column (C1), at least one pipe for sending the cooled synthesis gas to the column washing, a pipe for removing a hydrogen-enriched gas (19) at the top of the washing column, a column for discharging a liquid (23) enriched in carbon monoxide and / or methane from the washing column tank , a pipe for sending the tank liquid or a liquid (61) derived from the tank liquid, optionally after expansion, to a CO / CH4 separation column (C2), a pipe for withdrawing a liquid enriched in methane from the tank of the CO / CH4 separation column (25), a line for withdrawing a carbon monoxide enriched fluid from the head of the CO / CH4 separation column, means for pressurizing at least a portion of the carbon monoxide enriched fluid, , a pipe to send to the m oins part of the pressurized fluid at the head of the washing column, the washing column comprising a bottom reboiler (R1) for heating the tank of the washing column.
    公开号:FR3018599A1
    申请号:FR1452177
    申请日:2014-03-17
    公开日:2015-09-18
    发明作者:Bertrand Demolliens；Antoine Hernandez
    申请人:Air Liquide SA；LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a method and apparatus for separating a synthesis gas containing carbon monoxide, methane and hydrogen and optionally at least one hydrocarbon selected from the following list: ethane, propane, ethene , propene, butane, pentane. In particular, it relates to a process for separating, recovering and liquefying hydrocarbons contained in the synthesis gas. It is known to use methods of the methane washing type, described in EP-A-0 465 366, for separating a synthesis gas into its various constituents. This process is based in particular on the use of a fraction of a methane-rich fluid recovered in a CO / CH4 column tank as a washing fluid for the first two columns, the other fraction of this fluid then being recovered in the form of a purge. methane.
    [0002] By thermodynamic equilibrium between the washing methane and the overhead gas, part of the methane is then lost in the overhead gas. This will favor a CO wash, which will lower the methane content in the wash column overhead gas to maximize methane recovery.
    [0003] It is also known to produce carbon monoxide in liquid form, to bring it to the production pressure by means of a cryogenic pump and to vaporize it in the main exchange line in order to overcome a compressor of CO as described in WO-A-20080148971.The CO being pressurized to serve as a washing fluid, the CO fraction not used for washing can be directly produced under pressure to remix the gas exiting the first column. Some processes such as the Fischer Tropsch process make it possible to generate heavier hydrocarbons from elementary bricks such as carbon monoxide and hydrogen (especially gasoline). The presence of methane or an inert compound in the synthesis gas supplying the process is undesirable because the amount of gas to be treated is greater for the same gasoline production. Recovering light hydrocarbons in the synthesis gas upstream of a Fischer Tropsch process therefore has two advantages: - Advantage in the Fischer Tropsch process - Recovery of the hydrocarbons themselves in gaseous or liquid form (LNG) for a gasoline co-production light hydrocarbons. Some synthesis gases have a high percentage of light hydrocarbons in their composition, such as upstream of a Mark + type fixed bed and dry-bottom gasifier (FBDB®). A typical gas of this type comprises more than 12 mol% or even more than 15 mol% of methane. It is therefore interesting to propose a process for upgrading the hydrocarbons it contains. An object of the invention is to reduce the number of columns of the methane separation process (CO washing) described in US-A-4,488,890 or DE-A-2007062 213 from three columns to two. Another object of the invention is to increase product yield. The "stripping" column is here replaced by a reboiler in a CO washing column tank. The reboiler is fed either with the ring nitrogen or with Syngas itself. The wash column vessel will process a large liquid flow rate and a low gas flow rate while the wash column head will process a rather low liquid flow rate and a large gas flow rate. It can then be chosen to produce methane in gaseous form after it has been reheated in the exchange line or in liquid form after being sub-cooled in the exchange line. According to an object of the invention, there is provided a process for the cryogenic separation of a synthesis gas containing hydrogen, methane and carbon monoxide and optionally at least one hydrocarbon selected from the following list: ethane, propane, ethene, propene, butane, pentane and optionally nitrogen in which: i) the synthesis gas is cooled in a heat exchanger; ii) the cooled synthesis gas or at least one fluid derived from the synthesis gas is sent; cooled to a washing column iii) a hydrogen-enriched gas is discharged at the top of the washing column iv) a liquid enriched with carbon monoxide and / or methane is extracted from the wash column vessel; sends the vessel liquid or a liquid derived from the vessel liquid, optionally after expansion, to a separation column CO / CH4 vi) is withdrawn a methane-enriched liquid from the tank of the separation column CO / CH4 vii) is withdrawn an enriched fluid in carbon monoxide from the head of the CO / CH4 separation column viii) at least a portion of the carbon monoxide-enriched fluid is pressurized, the fluid can be a gas or a liquid, the fluid is liquefied if it is acts of a gas after or before pressurization, and sends at least a portion of the pressurized fluid to the head of the washing column characterized in that the tank of the washing column is heated by means of a bottom reboiler heated by means of a caloric gas. According to other optional features: the fluid is a carbon monoxide enriched liquid originating from the head of the CO / CH 4 separation column; the liquid which feeds the CO / CH 4 separation column is derived from the liquid of the reactor vessel; washing column by depleting nitrogen, for example by distillation - is vaporized a portion of the carbon monoxide enriched liquid from the head of the CO / CH4 separation column in the heat exchanger, optionally after pressurization. the synthesis gas comprises at least 12% or even 15% mol of methane. the heat-generating gas consists of at least a part of the synthesis gas or a cycle gas, for example nitrogen. - The liquid enriched in methane and optionally ethane or propane tank of the CO / CH4 separation column serves as the final product. at least a portion of the overhead gases of the washing column and at least a portion of the overhead gas of the CO / CH 4 separation column are mixed and sent to a Fischer-Tropsch conversion process or a process for the production of methanol. a carbon monoxide-rich gas from the CO / CH 4 separation column is compressed, compressed and condensed to serve as a washing liquid in the wash column; the process is kept cold by a cycle of carbon monoxide - the process is kept cold by a nitrogen cycle According to another object of the invention, there is provided an apparatus for cryogenic separation of a synthesis gas containing hydrogen, methane and monoxide of carbon and optionally at least one hydrocarbon selected from the following list: ethane, propane, ethene, propene, butane, pentane and optionally nitrogen comprising a heat exchanger in which the synthesis gas is cooled, a washing column, at least one conduit for sending the cooled synthesis gas or at least one fluid derived from the cooled synthesis gas to the wash column, a conduit for removing a hydrogen-enriched gas at the top of the wash column, a olonne for exiting a liquid enriched in carbon monoxide and / or methane from the tank of the washing column, a pipe for sending the tank liquid or a liquid derived from the tank liquid, possibly after expansion, to a separation column CO / CH4, a line for withdrawing a methane-enriched liquid from the tank of the CO / CH4 separation column, a line for withdrawing a carbon monoxide-enriched fluid from the head of the CO / CH4 separation column, means for pressurizing at least a portion of the carbon monoxide enriched fluid, the fluid being a gas or a liquid, means for liquefying the fluid if it is a gas after or before pressurization, a pipe for sending to the at least a portion of the pressurized fluid at the top of the washing column, characterized in that the washing column comprises a bottom reboiler for heating the tank of the washing column, the bottom reboiler being connected to a pipe ite of supply of a calorigenic gas. The CO / CH4 column may comprise a bottom reboiler and a top condenser.
    [0004] The apparatus described above may be combined with a Fischer Tropsch conversion or methanol production apparatus as well as means for mixing at least a portion of the overhead gas of the scrubbing column and at least a portion of the overhead gas of the CO / CH4 column, these means being connected to the inlet of the methanol conversion or production apparatus. The invention will be described in more detail with reference to the figures which show methods according to the invention. In Figure 1, the synthesis gas 1 contains CO2 and methanol, hydrogen, carbon monoxide, methane and at least one hydrocarbon selected from the following list: ethane, propane, ethene, propene, butane, pentane.
    [0005] The gas 1 may contain at least 12 mol% or even 15 mol% of methane. It can also contain at least 15 mol% of carbon monoxide. It may contain nitrogen. After purification in the adsorbent beds 3, the purified gas 7 is cooled in a heat exchanger 5. The partially condensed gas is sent to a phase separator 9. The gas 11 and the liquid 13 of the phase separator 9 are sent at different levels of a distillation column C1 which is a liquefied carbon monoxide wash column. A liquid 21 of the tank of the column C1 is vaporized in a reboiler R1 in order to increase the hydrogen / CO yield and to reduce the investment, because the process comprises only two columns. Another liquid 23 from the tank of the column C1 is sent to a column C2 after expansion in a valve Vl. A flow rich in methane and ethane is withdrawn from the tank of column C2 as the final product. Column C2 comprises a reboiler R2 and a condenser head RC1. Liquid carbon monoxide 27 is withdrawn at the top of the column C2 and is pressurized in a pump P1 to a pressure of at least .... The pressurized liquid is divided in two. A portion 29 is sent to the top of column Cl as a washing liquid. The remainder 31 vaporises under pressure in the heat exchanger 5 to provide a flow rate 31. The overhead gas 15 of the column C1, enriched with hydrogen, heats up in the heat exchanger 5. Part 17 of the heated gas serves to regenerate the adsorption beds and joins the rest to form the flow 19 rich in hydrogen. For the system of the figure, a nitrogen cycle is necessary to keep the process cold. Nitrogen from this cycle can be used to heat the reboiler R1. The carbon monoxide can come from the compression of carbon monoxide gas from the column C2 followed by its liquefaction to form the washing liquid. The phase separator 9 is not necessarily present. The gas 7 can cool to an intermediate level of the heat exchanger 5, reheat the reboiler R1 instead of the cycle nitrogen, while cooling partially, be cooled in the heat exchanger 5 until at the cold end and then be sent to column C1.
    [0006] It is possible to mix flow rates 19,31 to form a synthesis gas to be sent to a Fischer-Tropsch conversion or a methanol production. The flow rates 19 and 31 may be mixed, cold, at an intermediate level of the heat exchanger or after total heating in the exchanger.
    [0007] Figure 2 differs from Figure 1 in that a carbon monoxide cycle holds the process cold. The gaseous carbon monoxide 33 heats up in the heat exchanger 5, is compressed in a compressor A and is returned to cool in the heat exchanger. A part 35 of the cycle gas is expanded in a first turbine B and heated to be sent to the compressor A. Another part 37 taken at a cooler temperature of the exchanger 5 is expanded in a second turbine C where it condenses partially. After separation in a phase separator 41, the formed gas 37 is returned to the compressor A. The formed liquid is expanded in a valve V2 and mixes with the flow 39 from the compressor A which has cooled completely in the exchanger 5 and was expanded in a valve V3. The formed mixture 45 is sent to the condenser reboiler RC1. In Fig. 3, pump P1 is omitted since carbon monoxide is taken from column C2 in gaseous form. Carbon monoxide 33 in gaseous form heats up in the heat exchanger 5 and is compressed in the compressor A. Part 45 of the carbon monoxide serves as a product under pressure. The remainder 47 cools completely in the exchanger 5 where it condenses. The liquid is divided into two parts The portion 49 is expanded in the valve V2 is returned to the condenser RC1. The remainder 29 is expanded in the valve V3 and returned to the top of the column C1 to serve as washing liquid. Figure 4 differs from Figure 3 in that the overhead gas of column C2 is sent to a column C3 which is a denitrogenation column. In the column C3 comprising a tank reboiler R3 and an overhead condenser RC2, a carbon monoxide-rich liquid 55 is produced in the tank and vaporizes in the exchanger 5. The overhead gas 57 is enriched in nitrogen and heats up. 5. In FIG. 5, unlike FIG. 4, the denitrogenation takes place between the washing and the CO / CH4 separation. The denitrogenation column C3, having a reboiler and condenser as in FIG. 4, receives the vessel liquid 23 from the column 1, separating it to form a nitrogen-rich gas 57 and a nitrogen-depleted tank liquid 61. The liquid is then separated in column C2. In FIG. 6, the reheating of the bottom reboiler of FIG. 2 is carried out by the synthesis gas. The synthesis gas from the purification 3 and partially cooled in the exchanger 5 cools in the reboiler R1 and partially condenses. Sent to the phase separator 9, the gas 11 cools in the exchanger 5 and is sent to a second phase separator 9A. The gas 11A and the liquid 13A of the separator 9A are sent to separate in the column C1. The liquid 13 of the separator 9 is also sent to the separator 9A. It is the carbon monoxide cycle which heats the reboiler R2 of the column C2, the flow 37 cooling there before being sent to the turbine C.
    权利要求:
    Claims (10)
    [0001]
    REVENDICATIONS1. Process for the cryogenic separation of a synthesis gas containing hydrogen, methane and carbon monoxide and optionally at least one hydrocarbon selected from the following list: ethane, propane, ethene, propene, butane, pentane and optionally nitrogen in which: i) the synthesis gas is cooled in a heat exchanger (5) ii) the cooled synthesis gas or at least one fluid derived from the cooled synthesis gas is sent to a washing column (C1) iii a hydrogen-enriched gas (19) is discharged at the top of the washing column; iv) a liquid (23) enriched with carbon monoxide and / or methane is discharged from the tank of the washing column; tank liquid (23) or a liquid (61) derived from the tank liquid, optionally after expansion, at a separation column CO / CH4 (C2) vi) is withdrawn a liquid enriched in methane from the tank of the separation column CO / CH4 (25) vii) is withdrawn a fluid (27,33) enriched in my carbon monoxide from the top of the CO / CH4 separation column viii) at least a portion of the carbon monoxide-enriched fluid is pressurized, the fluid can be a gas or a liquid, the fluid (33) is liquefied if it is a gas after or before pressurization, and sends at least a portion of the pressurized fluid to the head of the washing column characterized in that the tank of the washing column is heated by means of a reboiler tank (R1), heated by means of a caloric gas (7).
    [0002]
    The method of claim 1 wherein the fluid is a carbon monoxide enriched liquid (27) from the head of the CO / CH4 (C2) separation column.
    [0003]
    3. Method according to claim 1 or 2 wherein is vaporized a portion of the carbon monoxide enriched liquid from the head of the CO / CH4 separation column in the heat exchanger (5), optionally after pressurization.
    [0004]
    4. Method according to one of the preceding claims wherein the synthesis gas (1,7) comprises at least 12% or even 15% mol of methane.
    [0005]
    5. Method according to one of the preceding claims wherein the calorigenic gas (7) is constituted by at least a portion of the synthesis gas or a cycle gas, for example nitrogen.
    [0006]
    6. Method according to one of the preceding claims wherein the liquid enriched in methane (25) and optionally ethane or propane of the tank of the CO / CH4 separation column serves as the final product.
    [0007]
    The method according to one of the preceding claims wherein at least a portion of the overhead gas (19) of the scrubbing column and at least a portion of the overhead gas (33) of the CO / CH4 column is mixed and sent to a Fischer-Tropsch conversion process or to a methanol production process.
    [0008]
    Apparatus for the cryogenic separation of a synthesis gas containing hydrogen, methane and carbon monoxide and optionally at least one hydrocarbon selected from the following list: ethane, propane, ethene, propene, butane, pentane and optionally nitrogen comprising a heat exchanger (5) in which the synthesis gas is cooled, a washing column (C1), at least one pipe for sending the cooled synthesis gas or at least one fluid derived from the synthesis gas cooled to the washing column, a pipe for outputting a hydrogen enriched gas (19) at the top of the washing column, a column for removing a liquid (23) enriched in carbon monoxide and / or methane from the reactor vessel. the washing column, a pipe for sending the tank liquid or a liquid (61) derived from the tank liquid, optionally after expansion, to a CO / CH4 separation column (C2), a pipe for withdrawing liquid enriched in methane from the c uve of the CO / CH4 separation column (25), a pipe for withdrawing a carbon monoxide enriched fluid from the head of the CO / CH4 separation column, means for pressurizing at least a portion of the monoxide-enriched fluid; carbon, the fluid being a gas or a liquid, means for liquefying the fluid if it is a gas after or before pressurization, a pipe for sending at least a portion of the pressurized fluid to the head of the column washing device characterized in that the washing column comprises a bottom reboiler (R1) for heating the tank of the washing column, the bottom reboiler being connected to a supply pipe for a caloric gas (7).
    [0009]
    9. Apparatus according to claim 8 wherein the CO / CH4 column (C2) comprises a bottom reboiler (R2) and a top condenser (RC1).
    [0010]
    An integrated apparatus comprising an apparatus according to one of claims 8 or 9 and a Fischer Tropsch conversion or methanol production apparatus and means for mixing at least a portion of the overhead gas (19) of the washing column. (C1) and at least a portion of the overhead gas (33) of the CO / CH4 column, these means being connected to the inlet of the methanol conversion or production apparatus.
    类似技术:
    公开号 | 公开日 | 专利标题
    JP2010501657A|2010-01-21|Method and apparatus for treating hydrocarbon streams
    JP2017536389A|2017-12-07|Method and apparatus for producing hydrocarbons
    AU2007200041B2|2009-03-26|Method and apparatus for producing products from natural gas including helium and liquefied natural gas
    FR3018599B1|2019-06-28|METHOD AND APPARATUS FOR CRYOGENIC SEPARATION OF A SYNTHESIS GAS CONTAINING CARBON MONOXIDE, METHANE AND HYDROGEN
    JP5469661B2|2014-04-16|Isobaric open frozen NGL recovery
    KR101265916B1|2013-05-22|cryogenic separation of synthesis gas
    JP2009533644A|2009-09-17|Natural gas stream liquefaction method and apparatus
    JP5551063B2|2014-07-16|Method and apparatus for separating a mixture of hydrogen, methane and carbon monoxide by cryogenic distillation
    US7071236B2|2006-07-04|Natural gas liquefaction and conversion method
    EP0968959A1|2000-01-05|Process for the production of carbon monoxide
    EP2932177A2|2015-10-21|Method and device for separating a mixture containing carbon dioxide by means of distillation
    JP2013511697A|2013-04-04|A method for separating nitrogen and carbon monoxide mixtures at cryogenic temperatures.
    US20120067081A1|2012-03-22|Process And Plant For Recovering Argon In A Separation Unit For A Purge Gas Used In The Synthesis Of Ammonia
    JP2016090138A|2016-05-23|Liquefaction natural gas manufacturing device and liquefaction natural gas manufacturing method
    EP3464171B1|2020-07-01|Method and facility for combined production of a mixture of hydrogen and nitrogen as well as carbon monoxide by cryogenic distillation and scrubbing
    FR3013106A1|2015-05-15|CRYOGENIC SEPARATION PROCESS FOR THE PRODUCTION OF A MIXTURE OF HYDROGEN AND NITROGEN CONTAINING LOW CO AND CH4 CONTENT
    US20210172678A1|2021-06-10|Method for generating refrigeration for a carbon monoxide cold box
    FR3097951A1|2021-01-01|METHOD AND APPARATUS FOR CRYOGENIC SEPARATION OF SYNTHESIS GAS FOR THE PRODUCTION OF CH4
    WO2019180374A1|2019-09-26|Method and appliance for separating a synthesis gas by cryogenic distillation
    FR3057056A1|2018-04-06|METHOD AND APPARATUS FOR RECOVERING ARGON IN A AMMONIA SYNTHESIS PURGE GAS SEPARATION UNIT
    FR3057942A1|2018-04-27|METHOD AND APPARATUS FOR CRYOGENIC SEPARATION OF A SYNTHESIS GAS BY PARTIAL CONDENSATION
    FR3058207A1|2018-05-04|PROCESS FOR CRYOGENIC SEPARATION OF A MIXTURE OF HYDROGEN AND CARBON MONOXIDE
    FR3058996A1|2018-05-25|METHOD AND INSTALLATION FOR CRYOGENIC SEPARATION OF A METHANE WASH MIXTURE
    FR2910603A1|2008-06-27|Carbon monoxide, hydrogen, methane and nitrogen mixture separating method, involves separating mixture at cold temperature by overhead condensation of carbon monoxide/methane separating column and boiling of discharge and separating columns
    WO2009013664A1|2009-01-29|Production of hydrocarbons
    同族专利:
    公开号 | 公开日
    WO2015140460A2|2015-09-24|
    FR3018599B1|2019-06-28|
    WO2015140460A3|2015-12-17|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4488890A|1982-12-23|1984-12-18|Linde Aktiengesellschaft|Low temperature separation of gaseous mixture for methanol synthesis|
    WO2008064762A2|2006-11-30|2008-06-05|Linde Aktiengesellschaft|Method and device for obtaining products from synthesis gas|
    DE102007013325A1|2007-03-20|2008-09-25|Linde Ag|Process and apparatus for recovering gas products and liquid methane from synthesis gas|
    WO2008148971A2|2007-05-04|2008-12-11|L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude|Method and device for separating a mixture of hydrogen, methane and carbon monoxide by cryogenic distillation|
    FR2930332A1|2008-04-18|2009-10-23|Air Liquide|METHOD AND APPARATUS FOR CRYOGENIC SEPARATION OF A MIXTURE OF HYDROGEN AND CARBON MONOXIDE|EP3599438A1|2018-07-25|2020-01-29|L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude|Method and device for cryogenic separation of a mixture of carbon monoxide, hydrogen and methane for the production of ch4|
    FR3097951A1|2019-06-26|2021-01-01|L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude|METHOD AND APPARATUS FOR CRYOGENIC SEPARATION OF SYNTHESIS GAS FOR THE PRODUCTION OF CH4|
    EP3783292A1|2019-08-20|2021-02-24|L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude|Method and device for producing carbon monoxide by partial condensation|FR2664263B1|1990-07-04|1992-09-18|Air Liquide|PROCESS AND PLANT FOR THE SIMULTANEOUS PRODUCTION OF METHANE AND CARBON MONOXIDE.|
    US6578377B1|2002-03-11|2003-06-17|Air Products And Chemicals, Inc.|Recovery of hydrogen and carbon monoxide from mixtures including methane and hydrocarbons heavier than methane|
    DE102007062213A1|2007-12-21|2009-06-25|Linde Ag|Production of hydrogen- and carbon monoxide-containing gas, i.e. oxo gas, from a mixture of these gases and methane, involves separation in a cryogenic stripper and scrubbing with liquid carbon monoxide|
    DE102012004047A1|2012-03-02|2013-09-05|Linde Ag|Method for producing e.g. gas product, involves carrying out decomposition in carbon dioxide product, and returning residual gas into carbon monoxide methane separation unit such that lossless methane process operation is performed|
    DE102012020469A1|2012-10-18|2014-04-24|Linde Aktiengesellschaft|Method for separating methane from methane-containing synthesis gas in separation unit, involves feeding capacitor with secondary portion of refrigerant of outlet temperature to intermediate temperature and cooling to lower temperature|CN112279217A|2020-11-03|2021-01-29|北京石油化工工程有限公司|Separation device and method for synthesis gas|
    法律状态:
    2016-03-21| PLFP| Fee payment|Year of fee payment: 3 |
    2017-03-22| PLFP| Fee payment|Year of fee payment: 4 |
    2018-03-23| PLFP| Fee payment|Year of fee payment: 5 |
    2019-03-22| PLFP| Fee payment|Year of fee payment: 6 |
    2020-12-18| ST| Notification of lapse|Effective date: 20201109 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1452177A|FR3018599B1|2014-03-17|2014-03-17|METHOD AND APPARATUS FOR CRYOGENIC SEPARATION OF A SYNTHESIS GAS CONTAINING CARBON MONOXIDE, METHANE AND HYDROGEN|
    FR1452177|2014-03-17|FR1452177A| FR3018599B1|2014-03-17|2014-03-17|METHOD AND APPARATUS FOR CRYOGENIC SEPARATION OF A SYNTHESIS GAS CONTAINING CARBON MONOXIDE, METHANE AND HYDROGEN|
    PCT/FR2015/050643| WO2015140460A2|2014-03-17|2015-03-17|Method and device for cryogenically separating a synthesis gas containing carbon monoxide, methane and hydrogen|
    [返回顶部]