CN110114626B - Process and apparatus for the cryogenic separation of synthesis gas by partial condensation - Google Patents

Process and apparatus for the cryogenic separation of synthesis gas by partial condensation Download PDF

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Publication number
CN110114626B
CN110114626B CN201780074179.7A CN201780074179A CN110114626B CN 110114626 B CN110114626 B CN 110114626B CN 201780074179 A CN201780074179 A CN 201780074179A CN 110114626 B CN110114626 B CN 110114626B
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synthesis gas
gas
carbon monoxide
separating
hydrogen
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CN110114626A (en
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阿克塞拉·盖特纳
安托万·埃尔南德斯
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Priority claimed from FR1660482A external-priority patent/FR3058207B1/en
Priority claimed from CN201621257756.5U external-priority patent/CN206831923U/en
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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
    • F25J3/0204—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
    • 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
    • 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
    • F25J3/0252—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
    • 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
    • F25J3/0261—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 carbon monoxide
    • 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
    • F25J3/0271—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
    • F25J2200/40—Features relating to the provision of boil-up in the bottom of a column
    • 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
    • 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
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/02—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum
    • 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
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/02—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum
    • F25J2205/04—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum in the feed line, i.e. upstream of the fractionation step
    • 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
    • F25J2270/02—Internal 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
    • F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/34—Details about subcooling of liquids
    • 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
    • F25J2290/40—Vertical layout or arrangement of cold equipments within in the cold box, e.g. columns, condensers, heat exchangers etc.

Abstract

In a process for separating a synthesis gas (1, 5) containing hydrogen and carbon monoxide, the synthesis gas is cooled in a heat exchanger (E), partially condensed and sent to a first phase separator (9) to produce a hydrogen-rich gas (7) and a hydrogen-depleted liquid (11), at least a portion of the hydrogen-depleted liquid is sent to the top of a stripping column (13), at least a portion of the bottom liquid (17) of the stripping column is at least partially vaporized into the heat exchanger, and a carbon monoxide-rich product is obtained from at least a portion of the bottom liquid of the stripping column.

Description

Process and apparatus for the cryogenic separation of synthesis gas by partial condensation
The present invention relates to a method and an apparatus for the cryogenic separation of synthesis gas by partial condensation.
The unit for the production of carbon monoxide and hydrogen can be divided into two sections:
-synthesis gas(mainly containing H)2、CO、CH4、CO2Ar and N2Of (2)Generation of. Among the various industrial routes for the production of synthesis gas, the route based on coal gasification seems to be increasingly enlarged, especially in countries rich in coal deposits, such as china. For H alone or at low2A process for the partial oxidation of natural gas with CO production at a/CO production ratio may also prove advantageous. Another route is steam reforming.
-Purification of synthesis gas. The following were found:
a unit for washing with a liquid solvent to remove the majority of the acid gases present in the synthesis gas,
-a unit for purging on the adsorbent bed,
a unit for the production of CO, separated by the cryogenic "cold box" route.
In the case of syngas production from entrained flow or fluidized bed gasification, the cold box process is partial condensation. For applications where the product from distillation is sent to the production of MEG (monoethylene glycol), TDI/MDI (toluene diisocyanate and/or methylene diphenyl diisocyanate), or PC (polycarbonate), it is desirable to include a device for separating CH in the cold box4The column of (1). The separation energy is provided by a recycle compressor as described in FR 2780391. The syngas is cooled to prevent vaporization in the low pressure cycle at a pressure equivalent to the compressor inlet pressure. The CO/CH4Column top condensation can be contributed by the evaporation of this cycle.
The invention uses a cold box with partial condensation of the synthesis gas, where the synthesis gas is cooled to prevent evaporation from the bottom of the stripper column at a pressure corresponding to the CO pressure directly generated, for example, at the pressure required for applications like the production of monoethylene glycol, polycarbonate or toluene diisocyanate, methylene diphenyl diisocyanate, which is typically between 5 and 9 bar.
Thus, no compressor or pump is required to compress the CO into the CO consuming device.
The cooling of the synthesis gas of the present invention is lower (warmer temperature) than in the state of the art, which results in a lower CO yield than obtained in the state of the art. In some cases, such as, for example, when the hydrogen-rich gas is sent to a methanol production unit, the carbon monoxide present in the hydrogen-rich gas is also upgraded in the methanol production unit.
CO/CH4Reflux at the top of the column is contributed by injecting a portion of the liquid from the bottom of the stripping column at the top of the column.
According to the subject of the invention, a process is provided for separating a synthesis gas containing hydrogen, carbon monoxide and optionally methane and/or nitrogen and/or argon, in which process:
i) the synthesis gas is cooled in a heat exchanger, partially condensed and sent to a first phase separator to produce a hydrogen-rich gas and a hydrogen-depleted liquid,
ii) after depressurization in a valve, the hydrogen-depleted liquid is at least partly sent to the top of a stripping column operating at a pressure between 6 and 20 bar absolute,
iii) the hydrogen-rich gas is reheated in the heat exchanger without depressurization or separation and is not recirculated to the synthesis gas,
iv) at least part of the bottom liquid from the stripping column is at least partially evaporated in the heat exchanger and optionally reheated until the warm end of the heat exchanger to form a gas,
v) the top gas from the stripping column is reheated in the heat exchanger without depressurization or separation and is not recycled into the synthesis gas,
and is
vi) the carbon monoxide rich gas is obtained from at least a portion of the bottom liquid from the stripper column without pressurizing the liquid or at least a portion of the gas prior to using it as a final product.
The final product is the product that is discharged from the process to be sent to the customer.
According to other optional aspects:
-at least a part of the bottom liquid from the stripping column, indeed all of the liquid, is sent to the heat exchanger so as to be evaporated in the heat exchanger without pressurizing it,
-separating the synthesis gas in a single-phase separator upstream of the stripper column,
the stripper column is a column equipped with plates or packing,
the first phase separator and, if appropriate, any further phase separator contain neither packing nor plates,
the synthesis gas contains methane and a portion of the bottom liquid from the stripping column is sent to a separation column to produce a gas rich in carbon monoxide and a liquid rich in methane, at least a portion of the bottom liquid contributing to the separation column the total condensation energy required at the top of the column,
-reheating all carbon monoxide rich gas in the heat exchanger to act as product,
-the carbon monoxide rich gas from the separation column is reheated in the heat exchanger without depressurization or separation and is not recycled to the synthesis gas,
the hydrogen-rich gas contains at least 20 mol% carbon monoxide, indeed even at least 25 mol% carbon monoxide,
-feeding the hydrogen-rich gas as feed gas to a unit for the production of methanol,
-producing a gas enriched in carbon monoxide in a yield of at most 80%, indeed even at most 75%,
the process comprises no stage of compressing the fluid other than optionally the synthesis gas upstream of stage i),
-the synthesis gas is reheated in the bottom of the stripping column and, if appropriate, in the bottom of the separation column upstream of the first phase separator,
no stream is depressurized in the turbine in the process,
-the process is not provided with a flow of cryogenic liquid from an external source,
all the liquid originating from the bottom of the stripping column ends up as process product after evaporation and optionally reheating without being pressurized as liquid or compressed as evaporated liquid.
According to another aspect of the present invention there is provided an apparatus for separating synthesis gas containing hydrogen, carbon monoxide and optionally methane and/or nitrogen and/or argon, the apparatus comprising a heat exchanger, a first phase separator, a stripping column, means for conveying synthesis gas to be cooled in the heat exchanger, means for feeding the partially condensed synthesis gas to the first phase separator to produce a hydrogen-enriched gas and a hydrogen-depleted liquid, means for discharging the hydrogen-enriched gas from the apparatus after reheating in the heat exchanger without depressurising it, separating it or recycling it with synthesis gas, means for feeding the hydrogen-depleted liquid at least partially to the top of the stripping column after depressurisation in a valve, means for discharging the top gas from the stripping column of the apparatus after reheating in the heat exchanger without depressurising it, Means for separating it or recycling it with the synthesis gas, means for conveying at least part of the bottom liquid from the stripping column to be at least partially evaporated in the heat exchanger and optionally to be reheated up to the warm end of the heat exchanger to form a gas, and means for obtaining carbon monoxide rich gas as end product from at least part of the bottom liquid from the stripping column, without connecting these means to a pump or compressor.
According to other optional aspects, the apparatus comprises:
-means for feeding all bottom liquid from the stripper column to the heat exchanger for evaporation thereof in the heat exchanger, without pressurizing means between the bottom of the stripper column and the heat exchanger,
-means for feeding a portion of the bottom liquid from the stripping column to the separation column to produce a gas enriched in carbon monoxide and a liquid enriched in methane,
-a separation column for producing a gas enriched in carbon monoxide and a liquid enriched in methane,
-means for conveying all carbon monoxide rich gas to be reheated in the heat exchanger to serve as product,
means for sending the hydrogen-rich gas as feed gas to a unit for producing methanol,
-no means for compressing the fluid other than the synthesis gas compressor, optionally upstream of the heat exchanger,
-the bottom of the stripping column contains a reboiler,
-the bottom of the separation column contains a reboiler,
means for feeding the synthesis gas to the reboiler of the stripping column and, if appropriate, to the reboiler of the separation column upstream of the first phase separator,
the plant does not contain a carbon monoxide cycle,
the plant comprises means for discharging all the gas rich in carbon monoxide as end product.
Optionally, the apparatus does not comprise a turbine.
The invention will be described in more detail with reference to the accompanying drawings, which show a method according to the invention.
In fig. 1, the partial condensation stage is followed by a stripping stage in column 13 operating between 6 and 20 bar absolute. The synthesis gas 1 containing hydrogen and carbon monoxide and optionally also methane and/or nitrogen and/or argon is purified in a purification unit 3 in order to remove water and/or methanol and/or carbon monoxide. The formed gas 5 is partly cooled in heat exchanger E and subsequently used to heat the liquid 23 of the bottom reboiler 21 of the stripper column 13. The gas thus cooled is further cooled until the cold end of the heat exchanger E, partially condensed and sent to a phase separator 9, where the liquid formed and the gas formed are separated. The stripper column is operated at a pressure between 6 and 20 bar absolute.
The hydrogen-rich gas 7 is discharged from the top of the phase separator and, without depressurization or separation, is sent to a unit for the production of methanol, in which carbon monoxide and hydrogen are reacted by catalysis to form methanol. The hydrogen-depleted liquid 11 is depressurized and sent to the top of a stripper column 13. The gas 15 formed at the top of the stripping column 13 is reheated in exchanger E without depressurization or separation. The liquid 17 is depressurized in a valve and evaporated in a heat exchanger E to form CO produced without pressurization.
According to the alternative form of fig. 1 shown in fig. 2, the liquid 17 from the bottom of the stripping column to be cooled in heat exchanger E is conveyed, discharged at the cold end, depressurized in valve 19 and separated in a second phase separator 27. The liquid 31 from the phase separator is reheated in heat exchanger E and combined with the gas 29 from the phase separator 27 to form carbon monoxide 33 produced by the plant.
In this figure 2, the cooling of the synthesis gas 5 heating the reboiler 21, starting from the intermediate temperature of the exchanger E, is not shown to simplify the figure. The cooling of the gas 5 is performed in the same way as in fig. 1.
In the case of synthesis gas containing methane, the bottom liquid 17 from the stripper column 13 in FIG. 1 containing methane and carbon monoxide is sent to the CO/CH4In the separation column 37, while passing through the column at CO/CH4A chamber 39 at the top of the column. Where a portion of the bottom liquid 17 is evaporated and discharged from the chamber as gas 43. The remainder 45 is discharged from the chamber and is divided into two parts. Part 49 is depressurized in a valve and fed as feed to the CO/CH4The top of the column 37. Thus, CO/CH4Reflux at the top of column 37 is contributed by the injection at the top of the column of a portion 49 of liquid 17 from the bottom of stripper column 13.
The residue 47 is depressurized in a valve to produce a partially condensed stream. The partially condensed stream is separated in phase separator 55 and the liquid and gas phases 59 and 57 are mixed to form stream 53, reheated to an intermediate temperature of heat exchanger E and returned as feed to the CO/CH4In the column 37. From CO/CH4The bottom of column 37 discharges a methane-rich liquid 42 and is subsequently evaporated in heat exchanger E. Carbon monoxide 41 as a gaseous product from CO/CH4The top of column 37 is discharged and reheated in heat exchanger E.
The distilled product may be sent to the production of MEG (monoethylene glycol), TDI/MDI (toluene diisocyanate and/or methylene diphenyl diisocyanate), or PC (polycarbonate).
An alternative to fig. 3 shown in fig. 4Not used in CO/CH4A chamber 39 at the top of the column 37. The bottom liquid 17 from the stripper column 13 is split into two portions. With part 61 as CO/CH4The top of the column is liquid-conducting. The residue 63 is depressurized in a valve, the resulting partially vaporized stream is separated in a phase separator 65, and the liquid phase 69 and the gas phase 67 are mixed, reheated to an intermediate temperature of heat exchanger E and returned as feed as stream 71 to the CO/CH4In the column 37. From CO/CH4The bottom of column 37 discharges a methane-rich liquid 42 and is evaporated in heat exchanger E. Carbon monoxide 41 as a gaseous product from CO/CH4The top of the column is discharged and reheated in heat exchanger E.
The syngas 5 of fig. 3 and 4 is first reheated in condenser/reboiler 21 with bottoms liquid from the stripper column and then reheated in condenser/reboiler 81 with bottoms liquid from the CO/CH prior to cooling to feed the phase separator 94The bottom of the column is liquid. Two condenser/reboilers may be fed in parallel from the synthesis gas.
In all examples, the synthesis gas to be separated is cooled by means of evaporation of the carbon monoxide rich liquid from the bottom of the stripping column, and the carbon monoxide rich gaseous product (after evaporation of the bottom liquid CO from the stripping column or at CO/CH)4Directly at the column outlet) is transported as product without compression.
The yield of carbon monoxide is typically about from 60% to 75%, whereas for the state of the art the yield is 75% -90%.
The invention makes it possible to operate without a CO compressor and to use the hydrogen-rich gas produced by partial condensation at the outlet of the first phase separator for the production of methanol (which requires H)2And CO) the loss of yield is not disadvantageous. The CO content in this gas may be at least 20 mol%, indeed even at least 25 mol%, compared to 10-15 mol% in the state of the art. This CO is upgraded in the production of methanol.
The CO purity in our invention is the same compared to the state of the art. For all these figures, the distilled product can be sent to the production of MEG (monoethylene glycol), TDI/MDI (toluene diisocyanate and/or methylene diphenyl diisocyanate), or PC (polycarbonate).
The method does not use any turbine and preferably does not use any contribution from cooling of the cryogenic liquid from an external source. In each figure, the cooling to partially condense the syngas is contributed by at least partial evaporation of the bottoms liquid from the stripper column. This evaporation is carried out at a single pressure.

Claims (30)

1. A process for separating synthesis gas (1, 5) containing hydrogen, carbon monoxide and optionally methane and/or nitrogen and/or argon, in which process:
i) cooling the synthesis gas in a heat exchanger (E), partially condensing and sending to a first phase separator (9) to produce a hydrogen-rich gas (7) and a hydrogen-depleted liquid (11),
ii) the hydrogen-depleted liquid is sent at least partially to the top of a stripping column (13) operating at a pressure between 6 and 20 bar absolute after depressurization in a valve,
iii) the hydrogen-rich gas is reheated in the heat exchanger without depressurization or separation and is not recirculated to the synthesis gas,
iv) at least part of the bottom liquid (17, 59, 69) from the stripping column is at least partially evaporated in the heat exchanger and optionally reheated until the warm end of the heat exchanger to form a gas,
v) the top gas (15) from the stripping column is reheated in the heat exchanger without depressurization or separation and is not recirculated to the synthesis gas,
and is
vi) a carbon monoxide rich gas (17, 29, 33, 41) is obtained from at least a part of the bottom liquid from the stripper column without pressurizing it before using at least a part of the liquid or the gas as final product,
wherein all carbon monoxide rich gas (17, 29, 33, 41) is reheated in the heat exchanger (E) to serve as product.
2. A process for separating synthesis gas (1, 5) according to claim 1, wherein at least a portion of the bottom liquid (17) from the stripper column (13) is sent to the heat exchanger (E) to be evaporated therein without pressurizing it.
3. Process for separating synthesis gas (1, 5) according to claim 1, wherein the bottom liquid (17) from the stripping column (13) is sent in its entirety to the heat exchanger (E) to be evaporated in it without pressurizing it.
4. A process for separating synthesis gas (1, 5) according to claim 1, wherein the synthesis gas contains methane and at least a portion (61, 63) of the bottom liquid (17) from the stripping column (13) is sent to a separation column (37) to produce a gas (41) enriched in carbon monoxide and a liquid (42) enriched in methane, at least a portion of the bottom liquid contributing to the separation column the total condensation energy required at the top of the column.
5. A method for separating synthesis gas (1, 5) according to claim 1, wherein the hydrogen rich gas (15) contains at least 20 mol% of carbon monoxide.
6. A method for separating synthesis gas (1, 5) according to claim 2, wherein the hydrogen rich gas (15) contains at least 20 mol% of carbon monoxide.
7. A method for separating synthesis gas (1, 5) according to claim 3, wherein the hydrogen rich gas (15) contains at least 20 mol% of carbon monoxide.
8. Process for separating synthesis gas (1, 5) according to claim 4, wherein the hydrogen rich gas (15) contains at least 20 mol% of carbon monoxide.
9. Process for separating synthesis gas (1, 5) according to claim 5, wherein the hydrogen rich gas (15) contains at least 25 mol% of carbon monoxide.
10. Process for separating synthesis gas (1, 5) according to claim 6, wherein the hydrogen rich gas (15) contains at least 25 mol% of carbon monoxide.
11. Process for separating synthesis gas (1, 5) according to claim 7, wherein the hydrogen rich gas (15) contains at least 25 mol% of carbon monoxide.
12. Process for separating synthesis gas (1, 5) according to claim 8, wherein the hydrogen rich gas (15) contains at least 25 mol% of carbon monoxide.
13. Process for separating synthesis gas (1, 5) according to any of claims 5 to 12, wherein the hydrogen rich gas (15) is fed as feed gas to a unit for the production of methanol.
14. The process for separating synthesis gas (1, 5) according to any of claims 1 to 12, wherein the gas enriched in carbon monoxide (17, 29, 33, 41) is produced in a yield of at most 80%.
15. Process for separating synthesis gas (1, 5) according to claim 13, wherein a gas (17, 29, 33, 41) enriched in carbon monoxide is produced in a yield of at most 80%.
16. Process for separating synthesis gas (1, 5) according to claim 14, wherein the gas enriched in carbon monoxide (17, 29, 33, 41) is produced in a yield of at most 75%.
17. Process for separating synthesis gas (1, 5) according to claim 15, wherein the gas enriched in carbon monoxide (17, 29, 33, 41) is produced in a yield of at most 75%.
18. Process for separating synthesis gas (1, 5) according to any one of claims 1 to 12, excluding the stage of compressing the fluid other than synthesis gas (1, 5) upstream of stage i).
19. Process for separating synthesis gas (1, 5) according to any one of claims 15 to 17, not comprising a stage of compressing a fluid other than synthesis gas (1, 5) upstream of stage i).
20. A method for separating synthesis gas (1, 5) according to any of claims 1-12, wherein the synthesis gas (1, 5) is reheated at the bottom of the stripper column (13).
21. Process for separating synthesis gas (1, 5) according to claim 19, wherein the synthesis gas (1, 5) is reheated at the bottom of the stripper column (13).
22. A method for separating synthesis gas (1, 5) according to any of claims 1-12, wherein the synthesis gas (1, 5) is reheated in the bottom of the stripper column (13) and in the bottom of a separation column (37) upstream of the first phase separator (9).
23. Process for separating synthesis gas (1, 5) according to claim 19, wherein the synthesis gas (1, 5) is reheated at the bottom of the stripping column (13) and at the bottom of a separation column (37) upstream of the first phase separator (9).
24. Process for separating synthesis gas (1, 5) according to any of claims 1 to 12, wherein no stream is depressurized in a turbine in the process.
25. Process for separating synthesis gas (1, 5) according to claim 21 or 23, wherein no stream is depressurized in a turbine in the process.
26. The process for separating synthesis gas (1, 5) according to any of claims 1 to 12, without using a carbon monoxide cycle to provide cooling.
27. The method for separating synthesis gas (1, 5) according to claim 25, without using a carbon monoxide cycle to provide cooling.
28. An apparatus for separating synthesis gas containing hydrogen, carbon monoxide and optionally methane and/or nitrogen and/or argon, the apparatus comprising a heat exchanger (E), a first phase separator (9), a stripping column (13), means for conveying synthesis gas to be cooled in the heat exchanger, means for feeding partially condensed synthesis gas into the first phase separator to produce a hydrogen-rich gas (7) and a hydrogen-depleted liquid (11), means for discharging the hydrogen-rich gas from the apparatus after reheating in the heat exchanger without depressurizing it, separating it or recycling it together with synthesis gas, means for feeding the hydrogen-depleted liquid at least partially to the top of the stripping column after depressurizing in a valve, means for discharging top gas (15) from the stripping column of the apparatus after reheating in the heat exchanger without depressurizing it, Means for separating it or recycling it with the synthesis gas, means for conveying at least a portion (59, 69) of the bottom liquid from the stripping column to be at least partially evaporated in the heat exchanger and optionally to be reheated up to the warm end of the heat exchanger to form a gas, and means for obtaining a carbon monoxide rich gas (17, 29, 33, 41) as a final product from at least a portion of the bottom liquid (17) from the stripping column, without connecting these means to a pump or compressor,
wherein the plant comprises means for discharging all carbon monoxide rich gas (17, 29, 33, 41) as end product.
29. The apparatus for separating a synthesis gas containing hydrogen, carbon monoxide and optionally methane and/or nitrogen and/or argon according to claim 28, comprising no carbon monoxide recycle.
30. An apparatus for separating a synthesis gas containing hydrogen, carbon monoxide and optionally methane and/or nitrogen and/or argon as claimed in claim 28 or 29, comprising a separation column (37) and means for sending a portion (53) of the bottom liquid (17) from the stripping column (13) to the separation column to produce a carbon monoxide rich gas (41) and a methane rich liquid (42).
CN201780074179.7A 2016-10-21 2017-10-19 Process and apparatus for the cryogenic separation of synthesis gas by partial condensation Active CN110114626B (en)

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FR1660209 2016-10-21
FR1660209A FR3057942B1 (en) 2016-10-21 2016-10-21 METHOD AND APPARATUS FOR CRYOGENIC SEPARATION OF A SYNTHESIS GAS BY PARTIAL CONDENSATION
FR1660482A FR3058207B1 (en) 2016-10-28 2016-10-28 PROCESS FOR CRYOGENIC SEPARATION OF A MIXTURE OF HYDROGEN AND CARBON MONOXIDE
FR1660482 2016-10-28
CN2016212577565 2016-11-22
CN201621257756.5U CN206831923U (en) 2016-11-22 2016-11-22 Equipment for separating the mixture containing hydrogen and carbon monoxide
PCT/FR2017/052879 WO2018073543A1 (en) 2016-10-21 2017-10-19 Method and equipment for cryogenically separating a synthesis gas by partial condensation

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