EP2147270B1 - Procédé et appareil de séparation d'un mélange d'hydrogène, de méthane et de monoxyde de carbone par distillation cryogénique - Google Patents

Procédé et appareil de séparation d'un mélange d'hydrogène, de méthane et de monoxyde de carbone par distillation cryogénique Download PDF

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EP2147270B1
EP2147270B1 EP08805696.5A EP08805696A EP2147270B1 EP 2147270 B1 EP2147270 B1 EP 2147270B1 EP 08805696 A EP08805696 A EP 08805696A EP 2147270 B1 EP2147270 B1 EP 2147270B1
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column
liquid
methane
head
mixture
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EP2147270A2 (fr
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Jean Billy
Antoine Hernandez
Marie-Khuny Khy
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Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0233—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of CnHm with 1 carbon atom or more
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0204—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the feed stream
    • F25J3/0223—H2/CO mixtures, i.e. synthesis gas; Water gas or shifted synthesis gas
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    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0252—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of hydrogen
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    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0271—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of H2/CO mixtures, i.e. of synthesis gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/70—Refluxing the column with a condensed part of the feed stream, i.e. fractionator top is stripped or self-rectified
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/72—Refluxing the column with at least a part of the totally condensed overhead gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/30—Processes or apparatus using other separation and/or other processing means using a washing, e.g. "scrubbing" or bubble column for purification purposes
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    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/06—Splitting of the feed stream, e.g. for treating or cooling in different ways
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2215/00—Processes characterised by the type or other details of the product stream
    • F25J2215/02—Mixing or blending of fluids to yield a certain product
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    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2215/00—Processes characterised by the type or other details of the product stream
    • F25J2215/04—Recovery of liquid products
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
    • F25J2230/24—Multiple compressors or compressor stages in parallel
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2235/00—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams
    • F25J2235/02—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams using a pump in general or hydrostatic pressure increase
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2245/00—Processes or apparatus involving steps for recycling of process streams
    • F25J2245/02—Recycle of a stream in general, e.g. a by-pass stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/12—External refrigeration with liquid vaporising loop
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/14—External refrigeration with work-producing gas expansion loop
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/20—Quasi-closed internal or closed external hydrogen refrigeration cycle
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/24—Quasi-closed internal or closed external carbon monoxide refrigeration cycle
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/30—Quasi-closed internal or closed external helium refrigeration cycle
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/42—Quasi-closed internal or closed external nitrogen refrigeration cycle
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/50—Quasi-closed internal or closed external oxygen refrigeration cycle
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/58—Quasi-closed internal or closed external argon refrigeration cycle
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/60—Closed external refrigeration cycle with single component refrigerant [SCR], e.g. C1-, C2- or C3-hydrocarbons
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/34—Details about subcooling of liquids

Definitions

  • the synthesis gas comprises a mixture at high pressure (between 15 and 60 bar) containing the following compounds: H 2 , CO, CH 4 , N 2 , Ar.
  • methane washing allows the production of pressurized hydrogen with good purity, whose CO content can range from 0.5% mol to a few ppm.
  • the residual content of CH 4 can not generally fall below 1 mol%.
  • US Patent 4488890 and US Patent 6098424 propose processes with a liquid carbon monoxide scrubbing column in which substantially all the frigories are produced by a carbon monoxide cycle.
  • the idea is to cool the synthesis gas to a similar temperature level. of -167 ° C (thus 20 ° warmer than in a partial condensation scheme), the vapor phase being treated in a CO washing column where liquid CO is injected at the top of the column.
  • WO2008 / 113494 form part of the state of the art with respect to novelty and discloses a process according to claim 1 except that the refrigeration cycle does not include two vaporization steps at different pressures.
  • synthesis gas 1 available under high pressure (generally between 15 and 60 bar) is cooled in the main exchanger 3 and partially condensed in the exchange line to a temperature level of the order of -167 ° vs.
  • the vapor phase is sent to the bottom of a washing column 5 where it is washed with liquid CO 51 injected at the top of the column 5. This makes it possible to lower the CH 4 content in the steam 7 produced at the top of the column 5. washing column 5 to less than 1 mol% to be able to treat after heating in the exchange line in a unit of MeOH for example.
  • the liquid phase 11, in the liquid CO column 5, is very rich in CH 4 and also contains CO and dissolved hydrogen.
  • This liquid 11 is sent to the top of a depletion column 13, having a bottom reboiler 15, to separate hydrogen and lower its content in the flash column tank liquid 17 to reduce the amount of hydrogen. incondensable hydrogen during CO and CH 4 separation in column 33.
  • the leading gas 21 of the exhaustion column heats up in the line exchange 3 and serves as fuel.
  • the bottom liquid 17 of the depletion column 13 is subcooled by the exchanger 19 and is then sent to a two-part CO / CH 4 separation column.
  • a portion 27 is expanded in the valve 31 and sent to the top of the column 33.
  • the remainder 23 is expanded in the valve 29, then heated by the heater 25 and then sent to the bottom of the column 33.
  • the CO is produced in liquid form 47 at the head and is sent to pumps 49 to raise its pressure up to the pressure level of the CO 5 washing column.
  • a portion of the liquid CO 55 may be passed through the overhead gas valve 57 of the washing column 5 to form a mixed flow rate 9. This allows the CO / H 2 ratio of the gas to be adjusted.
  • CH 4 39 is produced in a CO / CH 4 33 column vat in liquid form.
  • the column CO / CH 4 has a bottom reboiler 37 and a top condenser 35.
  • This CH 4 liquid 39 output tank CO / CH 4 column will be subcooled in the exchange line 41 before sending it to storage to limit the production of vaporized liquid said boil off.
  • a valve 43 makes it possible to short-circuit the line 41.
  • overhead gas 59 of column CO / CO 4 33 is compressed in a compressor 61 to form flow 63, condensed in the exchange line and sent to the top of the washing column 5 in place of or in addition to the pumped flow from the pump 49.
  • the separation energy is provided by a closed external cycle. This cycle will also bring the liquefaction energy of this CH 4 39.
  • the gas used for the cycle can be chosen from the list N 2 , CH 4 , O 2 , Ar, He, H2 ....
  • the gas 65 serves to reboil the CO / CH 4 column and then forms the liquid 67 which is divided in two.
  • a portion 71 passes through the valve 73 and is sent to the head condenser 35.
  • the vaporized flow rate in the condenser is sent as flow 81, 83 to the series compressor 85, 87, 89.
  • the flow 91 compressed in the compressor 89 is divided into two portions 93, 95 which are compressed into two compressors 97, 99 in parallel.
  • the compressed flow rates 95, 101 are combined to form a flow 103 which is divided in two.
  • Part 105 is partially cooled in the exchange line 3 before being divided into two.
  • a fraction 109 is expanded to an intermediate temperature in the turbine 111 and the expanded flow rate 113 is returned to the flow 81 at an intermediate temperature level of the exchange line 3.
  • the other fraction is sent to the turbine 115 at a level of temperature lower than the cooling temperature of the 109 of the exchange line 3 and reaches the flow 81 upstream of the exchange line 3.
  • the flow 107 cools completely in the exchange line 3 and is sent in as debit 65 reboil CO / CH4 column.
  • Spraying flow rates 77, 81 in the exchanger 3 at two different pressures optimizes the heat exchange.
  • synthesis gas 1 available under high pressure contains 15 mol%. of methane. It is divided in two, a part 1A being cooled in the main heat exchanger 3 and the rest 1B bypassing the main heat exchanger before being remixed with the flow 1A and sent to the bottom reboiler 37 of the column CO / CH 4 33 like the flow 3 circled.
  • the encircled flow rate 4 cooled in the bottom reboiler is returned to an intermediate level of the main exchanger 3 and partially condensed in the exchange line to a temperature level of the order of -167 ° C. It is sent to the bottom of a washing column 5 where it is washed with liquid CO 51 injected at the top of the column 5. This makes it possible to lower the CH 4 content in the steam 7 produced at the top of the washing column. 5 to less than 1 mol%. to be able to treat it after heating in the exchange line in a unit of MeOH for example.
  • the liquid phase 11, in the liquid CO column 5, is very rich in CH 4 and also contains CO and dissolved hydrogen.
  • This liquid 11 is sent to the top of a depletion column 13, having a bottom reboiler 15, to separate hydrogen and lower its content in the flash column tank liquid 17 to reduce the amount of hydrogen. incondensable hydrogen during CO and CH 4 separation in column 33.
  • the overhead gas 21 of the depletion column heats up in the exchange line 3 and serves as fuel.
  • the bottom liquid 17 of the depletion column 13 is subcooled by the exchanger 19 and is then sent to a two-part CO / CH 4 separation column.
  • a portion 27 is expanded in the valve 31 and sent to the top of the column 33.
  • the remainder 23 is expanded in the valve 29, and then heated by heating 25 and then sent to the lower part of column 33.
  • the CO is produced in liquid form at the top and is sent to pumps 49 to raise its pressure up to the pressure level of the CO 5 scrubbing column. therefore an internal loop of liquid CO through at least one cryogenic pump 49 and a valve 53 between the CO / CH 4 column head 33 and the CO 5 scrub head.
  • a portion of the liquid CO 55 can be passed through the valve 55 to the overhead gas 7 of the washing column 5 to form a mixed flow 9. This allows to adjust the CO / H 2 ratio of the gas.
  • CH 4 39 is produced in a CO / CH 4 33 column vat in liquid form.
  • the column CO / CH 4 has a bottom reboiler 37 and a top condenser 35.
  • This CH 4 liquid 39 outlet column CO / CH 4 will be subcooled in the exchange line 41 before sending it to storage to limit the production of vaporized liquid called boa off.
  • a valve 43 makes it possible to short-circuit the line 41.
  • the overhead gas 59 of the CO / CO 4 33 column is compressed in a compressor 61 to form the flow 63, condensed in the exchange line 3 and sent to the top of the washing column 5 in addition to the pumped flow from pump 49.
  • the separation energy is provided by a closed external cycle. This cycle will also bring the liquefaction energy of this CH 4 39.
  • the gas used for the cycle can be chosen from the list N 2 , CH 4 , O 2 , Ar, He, H 2
  • the reboiling of the depletion column 13 is ensured by a cycle gas flow rate 169.
  • the cooled flow rate 171 is expanded in a valve 173 and sent to the head condenser 35 of the CO / CH 4 column 33 as the flow rate.
  • the flow 175 is divided to form the flow rates 177 and 179.
  • the flow 177 cools the condenser 35.
  • the flow 179 is passed through the valve 181 to the exchanger 3 where it heats up.
  • the flow 180 heated in the reboiler 35 is mixed with the flow rates 167 and 194 to become the flow 183. This flow 183, when slightly warmed mixes with the flow 179.
  • the mixed flow 185 at 10-bar is sent to the compressors cycle 85,87 in series and then in part of the compressor 89.
  • a portion 169 of the 89 compressed flow rate is sent to 39 bars at the reboiling of the column 13 and the remainder 191 is compressed in the compressor 197 at 50 bar to form the flow 201.
  • Debit 201 is divided into two to form the flow 203 which goes through the valve 205 to the turbine 211 to become the expanded flow rate 167.
  • the flow 202 passes entirely through the exchanger 3 and is divided into three.
  • the flow 190 is sent to the turbine 211 too, the flow 174 is mixed with the flow 171 and the flow 186 is heated in the exchanger 3 before being mixed with the flow 192 from the compressor 87 to form a mixed flow 189.
  • the flow 189 is sent to the compressor 199, cools partially in the exchanger 3 and is expanded in the turbine 215 to form the expanded flow 194.
  • the compressor 197 is coupled to the turbine 211 and the compressor 199 is coupled to the turbine 215.
  • top of column includes positions ranging from the head of the column stricto sensu to a position at most 10 theoretical plateaux below this position.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Separation By Low-Temperature Treatments (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Hydrogen, Water And Hydrids (AREA)
EP08805696.5A 2007-05-04 2008-04-23 Procédé et appareil de séparation d'un mélange d'hydrogène, de méthane et de monoxyde de carbone par distillation cryogénique Active EP2147270B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0754859A FR2915791B1 (fr) 2007-05-04 2007-05-04 Procede et appareil de separation d'un melange d'hydrogene, de methane et de monoxyde de carbonne par distillation cryogenique
PCT/FR2008/050742 WO2008148971A2 (fr) 2007-05-04 2008-04-23 Procede et appareil de separation d'un melange d'hydrogene, de methane et de monoxyde de carbone par distillation cryogenique

Publications (2)

Publication Number Publication Date
EP2147270A2 EP2147270A2 (fr) 2010-01-27
EP2147270B1 true EP2147270B1 (fr) 2019-11-06

Family

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EP08805696.5A Active EP2147270B1 (fr) 2007-05-04 2008-04-23 Procédé et appareil de séparation d'un mélange d'hydrogène, de méthane et de monoxyde de carbone par distillation cryogénique

Country Status (6)

Country Link
US (1) US20100162754A1 (zh)
EP (1) EP2147270B1 (zh)
JP (1) JP5551063B2 (zh)
CN (1) CN101688753B (zh)
FR (1) FR2915791B1 (zh)
WO (1) WO2008148971A2 (zh)

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Publication number Priority date Publication date Assignee Title
CN102353233B (zh) * 2011-08-03 2014-05-07 成都蜀远煤基能源科技有限公司 煤制气甲烷化后气体深冷分离液化的工艺方法和装置
CN102288008B (zh) * 2011-08-04 2013-06-12 成都蜀远煤基能源科技有限公司 煤制气来原料气的一氧化碳提取方法
CN102674347A (zh) * 2012-05-17 2012-09-19 四川亚连科技有限责任公司 一种低温蒸馏制备一氧化碳的方法
FR3018599B1 (fr) 2014-03-17 2019-06-28 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procede et appareil de separation cryogenique d’un gaz de synthese contenant du monoxyde de carbone, du methane et de l’hydrogene
FR3052159B1 (fr) * 2016-06-06 2018-05-18 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procede et installation pour la production combinee d'un melange d'hydrogene et d'azote ainsi que de monoxyde de carbone par distillation et lavage cryogeniques
FR3057056B1 (fr) * 2016-10-03 2020-01-10 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procede et appareil de recuperation d’argon dans une unite de separation d’un gaz de purge de synthese d’ammoniac
CN107417495A (zh) * 2017-05-27 2017-12-01 李大鹏 一种煤制甲醇、lng、液体燃料的多联产方法及装置
FR3084453B1 (fr) 2018-07-25 2020-11-27 Air Liquide Procede et appareil de separation cryogenique d'un melange de monoxyde de carbone, d'hydrogene et de methane pour la production de ch4
FR3097951B1 (fr) 2019-06-26 2022-05-13 Air Liquide Procede et appareil de separation cryogenique d’un gaz de synthese pour la production de ch4

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US4727723A (en) * 1987-06-24 1988-03-01 The M. W. Kellogg Company Method for sub-cooling a normally gaseous hydrocarbon mixture
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Also Published As

Publication number Publication date
CN101688753A (zh) 2010-03-31
JP5551063B2 (ja) 2014-07-16
EP2147270A2 (fr) 2010-01-27
CN101688753B (zh) 2013-08-14
WO2008148971A2 (fr) 2008-12-11
US20100162754A1 (en) 2010-07-01
JP2010526271A (ja) 2010-07-29
WO2008148971A3 (fr) 2010-01-07
FR2915791B1 (fr) 2009-08-21
FR2915791A1 (fr) 2008-11-07

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