EP2906502A2 - PROCÉDÉ ET INSTALLATION DE PRODUCTION D'UN FLUX DE PRODUIT H2 ET D'UN FLUX DE PRODUIT CO& xA; - Google Patents

PROCÉDÉ ET INSTALLATION DE PRODUCTION D'UN FLUX DE PRODUIT H2 ET D'UN FLUX DE PRODUIT CO& xA;

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Publication number
EP2906502A2
EP2906502A2 EP13734667.2A EP13734667A EP2906502A2 EP 2906502 A2 EP2906502 A2 EP 2906502A2 EP 13734667 A EP13734667 A EP 13734667A EP 2906502 A2 EP2906502 A2 EP 2906502A2
Authority
EP
European Patent Office
Prior art keywords
gas
stream
feed stream
separator
ratio
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13734667.2A
Other languages
German (de)
English (en)
Inventor
Thomas Trott
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Linde GmbH
Original Assignee
Linde GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Linde GmbH filed Critical Linde GmbH
Publication of EP2906502A2 publication Critical patent/EP2906502A2/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/506—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification at low temperatures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • 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
    • F25J3/0252—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/042—Purification by adsorption on solids
    • C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/046—Purification by cryogenic separation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/047—Composition of the impurity the impurity being carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/146—At least two purification steps in series
    • C01B2203/147—Three or more purification steps in series
    • 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
    • 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
    • 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
    • F25J2205/40—Processes or apparatus using other separation and/or other processing means using hybrid system, i.e. combining cryogenic and non-cryogenic separation techniques
    • 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
    • F25J2205/60—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
    • 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
    • F25J2205/60—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
    • F25J2205/66—Regenerating the adsorption vessel, e.g. kind of reactivation 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
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/02—Multiple feed streams, e.g. originating from different sources
    • 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
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/04—Mixing or blending of fluids with the feed 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
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/42—Nitrogen
    • 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
    • F25J2220/00—Processes or apparatus involving steps for the removal of impurities
    • F25J2220/02—Separating impurities in general from the feed 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
    • F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
    • F25J2230/32—Compression of the product 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
    • 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
    • F25J2270/04—Internal 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
    • F25J2270/24—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
    • F25J2280/00—Control of the process or apparatus
    • F25J2280/02—Control in general, load changes, different modes ("runs"), measurements

Definitions

  • the invention relates to a method and a system for generating an H 2 product stream and a CO product stream from one or more
  • Feedstreams comprising H 2 and CO (eg synthesis gas,
  • Rohkohlenmonoxid In such processes is usually a synthesis gas, which usually has H 2 , CO, CH 4 , C0 2 and in particular also inert gases (N 2 and Ar), from a synthesis gas, which usually has H 2 , CO, CH 4 , C0 2 and in particular also inert gases (N 2 and Ar), from a synthesis gas, which usually has H 2 , CO, CH 4 , C0 2 and in particular also inert gases (N 2 and Ar), from a synthesis gas, which usually has H 2 , CO, CH 4 , C0 2 and in particular also inert gases (N 2 and Ar), from a synthesis gas, which usually has H 2 , CO, CH 4 , C0 2 and in particular also inert gases (N 2 and Ar), from a synthesis gas, which usually has H 2 , CO, CH 4 , C0 2 and in particular also inert gases (N 2 and Ar), from a synthesis gas, which usually has H 2 , CO, CH 4 , C0 2
  • Discharge unit eg partial oxidation
  • purified C0 2 / H 2 0- removal
  • decomposed into its components, preferably in a CO product stream, a H 2 product stream, a flash gas and in particular a tail gas.
  • Such a decomposition is preferably carried out by rectification in a cryogenic
  • Separating device which may be arranged for example in a so-called cold box, which isolates the components of the separator to the outside, so that any cold losses or heat inputs are minimized.
  • the separation of the synthesis gas in the separator in its individual components is preferably carried out at high operating pressures and low H 2 / CO ratio and
  • Methane content in the feed gas preferably by partial condensation.
  • the H 2 fraction (gas fraction) withdrawn from the separating device can subsequently be cleaned in a pressure swing adsorption device (DWA, PSA) in order to obtain the said H 2 product.
  • DWA, PSA pressure swing adsorption device
  • Pressure swing adsorber and the tail gas and flash gas from the cryogenic separator are usually fired to produce steam or electricity. These currents thus represent losses of CO and H 2.
  • the above-described separation of the constituents of the synthesis gas by means of partial condensation usually can not be achieved over a wide range of the H 2 / CO ratio or with significantly different feed gases, such as, for example, synthesis gas or crude carbon monoxide. be performed.
  • the CO recovery rate (yield) of the partial condensation is usually 75% to 85%.
  • a CO recovery rate in the range of 90% can be regularly achieved only when the temperature in the separator is about 70 K, which is only possible with very complex and costly insulation (cold box) and piping within the separator.
  • the present invention therefore based on the problem to provide a method of the type mentioned above, which has a comparatively high recovery rate for CO, in particular, should be made possible that feed streams with a wide range of H 2 / CO ratios to
  • Production of said products can be used.
  • the process according to the invention then comprises the steps of: feeding a feed stream (feed gas) comprising H 2 and CO into a (cryogenic) separating device, which is preferably arranged in a so-called cold box,
  • the H 2 -rich gas fraction for separating CO and possibly other undesirable components such as CH 4 , C0 2 , H 2 0 are passed through at least one adsorber of a DWA, so that said Components are adsorbed on the adsorber and correspondingly from the remaining gas fraction of the H 2 product stream is formed, wherein the adsorber for purging the adsorber or the Druckcicadsorptions adopted with a hydrogen-containing purge gas / purge gas (in particular a partial stream of the H 2 - product stream) is rinsed, which is then withdrawn from the DWA, said purge gas and the flash gas upstream of the separator in the
  • the H 2 -rich gas fraction, the flash gas, and if needed a partial stream of the CO product stream (in particular after compression) upstream of the separator into the feed stream are fed.
  • the aforementioned recirculation measures reduce the losses of CO and H 2 to the quantities contained in the tail gas of the separator. As a result, the recovery rates for CO and H 2 are significantly increased. The consumption of feed streams (synthesis gas or raw carbon monoxide) decreases accordingly.
  • the inventive method allows adjustment of the H 2 / CO ratio upstream of the separator.
  • two different feed streams eg synthesis gas and / or raw carbon monoxide
  • feed stream can be used either individually or in mixed form as feed stream. This makes it possible, in particular, to switch from a first feed stream to a second feed stream (and back) during operation of the plant, ie while the process is running while maintaining the product qualities.
  • the instantaneous H 2 / CO ratio of the feed stream is continuously (repeatedly) measured upstream of the separator and the feed stream consisting of synthesis gas, raw carbon monoxide, recycle gases (flash gas, DWA purge gas and / or crude H2 and / or product CO from Cold Box) and if necessary hydrogen (from the plant boundary or from bottles) mixed so that the current H 2 / CO ratio equalizes a predefinable setpoint or is regulated within a predefined range.
  • a raw carbon monoxide stream (eg from a preceding separation device or from another preceding process step) usually has a concentration of CO in the range from 95 mol% to 99 mol% and also hydrogen a concentration in the range of 0.1 mol% to 5mol% and correspondingly further constituents such as CH 4 (0.1 mol% - 1, 0 mol%) and inert gases (N 2 and argon: balance). Accordingly, said threshold may be such that at
  • the H 2 -rich gas fraction and the flash gas from the separator and possibly a portion of the CO-Produkstromes as described above can be recycled.
  • the feed stream is formed by a synthesis gas in which, in particular, the H 2 / CO ratio exceeds said threshold and the crude H 2 is driven to the DWA.
  • the feed stream may of course be a mixture of a synthesis gas stream and a crude carbon monoxide stream to adjust a desired H 2 / CO ratio and thus a desired H 2 / CO product ratio.
  • the DWA purge gas and the flash gas is preferably via a compressor as
  • Feed stream is supplied upstream of the separator, whereas said flash gas is returned to the feed stream only via the subsequent second section.
  • Rohkohienmonoxidstrom is used as feed stream or the H 2 / CO ratio is less than or equal to said threshold, the H 2 -rich gas fraction and the flash gas from the separator and, if necessary, a part of the CO product stream through the second section of the compressor recycled as recycle stream in the feed stream upstream of the separator.
  • Compressor be switched off to save energy, especially if the system longer than a predeterminable period of time with the said
  • the feed stream is dried before being fed into the separating device in an adsorption stage (drying unit) and freed from C0 2 .
  • a corresponding, loaded adsorber of the adsorption can be z. B. be regenerated with N 2 , z. B. if the C0 2 - and H 2 0 concentration in the feed gas only a few mol ppm.
  • the recycle stream or the recycled components of the feed stream are cooled by means of a heat exchanger downstream of the compressor (compressor aftercooler).
  • compressor aftercooler downstream of the compressor
  • Adsorption be detected a current actual temperature of the feed stream, wherein preferably in the event that this actual temperature is less than or equal to a predefinable setpoint temperature (reference temperature), the recirculation flow is at least partially past said heat exchanger, d. H. the heat exchanger is not flowed through by a partial flow of the recycle stream (bypass). In this way, the actual temperature of the feed stream can be adjusted to the given target temperature.
  • a predefinable setpoint temperature reference temperature
  • an additional hydrogen feed stream is added upstream of the separator or upstream of the adsorption for setting said ratio in the feed stream.
  • the separator are introduced into a H wherein the H 2 -rich Flash Gas 2 -Strippkolonne is withdrawn from the top of the H, whereas the CO-product stream from the bottom said column is withdrawn.
  • said CO product stream can pass through more columns to z. B. CH 4 and N 2 from the CO-rich product stream to separate.
  • said separating means is arranged for cryogenic splitting of the feed stream in a cold box or formed as such.
  • a cold box usually has a metal jacket, which on a
  • Piping the cold box and its components carries (separator).
  • the interior of the cold box or the sheet metal box is usually with a
  • Insulating material filled to reduce the heat input into the cold box.
  • Separator or the cold box has, in addition to the separators and columns for separating the feed stream one or more heat exchangers, with the aid of which the feed stream is cooled against process streams (decomposition products).
  • process streams decomposition products
  • Gas fraction and a CO-rich, H 2 -containing condensate, the separator z. B. have a separator (as in the condensation process). However, such a separation can also be realized by a methane wash column (as in the Methanskysche).
  • the plant according to the invention comprises a separation device, which is set up and provided, a feed stream having H 2 and CO (eg synthesis gas, raw carbon monoxide, a mixture thereof or a mixture of two synthesis gases), in a H 2 -rich, CO -containing gas fraction (crude H2) and a CO-rich, H 2 -containing condensate, wherein the separating device is further adapted and provided, the said condensate in a H 2 -riches Flash gas and the CO product stream (and in particular a CH 4 - and / or N 2 -rich tail gas) to separate and wherein the separating device is arranged in particular in a cold box, which may be formed as set forth above.
  • H 2 and CO eg synthesis gas, raw carbon monoxide, a mixture thereof or a mixture of two synthesis gases
  • the separating device is further adapted and provided, the said condensate in a H 2 -riches Flash gas and the CO product stream (and in particular a CH
  • a means for determining the H 2 / CO ratio of the feed stream upstream of the separating device, in particular upstream of an adsorption stage is provided. This makes it possible to switch the system back and forth between two or more modes (H 2 / CO ratios) and to mix the feed and recycle streams.
  • the plant is preferably configured to have a H 2 / CO ratio of
  • Synthesis gas is used as feed stream) the H 2 -rich gas fraction to
  • the system is preferably designed to be at an H 2 / CO ratio, which is less than or equal to the aforementioned threshold (if, for example, a Rohkohienmonoxidstrom is used as feed stream), the flash gas and possibly a portion of the CO product stream and the said H2 -rich gas fraction upstream of the separator or upstream of an adsorption step (see above) in the feed line (ie in the feed stream) to return.
  • the invention enables, in particular, a significant increase in the CO and H 2 recovery rates over the entire plant, which leads to a reduction of operating costs for feed gases and equipment and investment costs through a smaller plant (saving in capex and opex)
  • FIG. 1 shows a schematic representation of a system according to the invention
  • Product yields from a feed stream in particular synthesis gas and / or raw carbon monoxide.
  • FIG. 1 shows a schematic block diagram of a plant 1 for producing an H 2 product stream and a CO product stream or a corresponding process.
  • the plant 1 has a feed line 2, via the synthesis gas E via a
  • Heat exchanger 60 is fed as a feed stream E "via a line 200 into an adsorption stage 10. Furthermore, the plant 1 has a further feed line 3, via which a Rohkohienmonoxidstrom E 'via a controllable valve 4 in the said Line 200 can be given so that a resulting feed stream E "can be a mixture of the said synthesis gas E and the raw carbon monoxide E ', whereby such a raw carbon monoxide stream E' preferably has only traces of CO 2 or H 2 O, each of which is less than 2 mol ppm. Such a raw carbon monoxide stream E 'can be withdrawn, for example, from an upstream cold box which is connected to feed line 3.
  • the feed stream E "thus has a certain (adjustable) H 2 / CO ratio, wherein on the line 200, an agent (sensor) 70 is arranged, which is adapted to detect a current actual value of the H 2 / CO ratio and to pass it on to a first control means 71, which is designed to open or close the controllable valve 4, in order to adapt the actual value of the H 2 / CO ratio to a desired desired value.
  • an agent (sensor) 70 is arranged, which is adapted to detect a current actual value of the H 2 / CO ratio and to pass it on to a first control means 71, which is designed to open or close the controllable valve 4, in order to adapt the actual value of the H 2 / CO ratio to a desired desired value.
  • the means 70 for detecting the said H 2 / CO ratio forwards the instantaneous actual value of that ratio to a further, second control means 72 which cooperates with the first control means 71, the second control means 72 being designed to have a further controllable valve 73 a supply line 73 to open or close, via which a hydrogen stream W downstream of the
  • Heat exchanger 60 can be placed in the line 200, in accordance with the said actual value to the predetermined setpoint of the H 2 / CO ratio
  • the feed stream is passed via the line 200 into an adsorption stage 10, in which H 2 O and optionally C0 2 are removed from the feed stream E ", in particular an adsorber used for this purpose by means of a nitrogen stream 5
  • H 2 O and optionally C0 2 are removed from the feed stream E ", in particular an adsorber used for this purpose by means of a nitrogen stream 5
  • Adsorption 10 withdrawn feed stream E "is then over another Line 201 is passed into a separating device 20, which is preferably arranged in a cold box, and is set up and provided to cryogenically separate the components of the feed stream E "from one another (for example by means of partial
  • the feed stream E is compared to existing process streams (eg, decomposition products) in at least one
  • a corresponding tail gas T (predominantly containing CH 4 and / or N 2 ) is then withdrawn via a line 24 from the separator 20.
  • a separation into the H 2 -rich gas fraction and the CO-rich condensate can also be carried out by means of a methane wash column.
  • the CO product stream P "thus formed is withdrawn from the separator 20 and fed via a line 25 to a compressor 28 and is then available for further processing, if desired, a portion of the compressed CO product stream (via line 26) as CO Cycle for cooling (Joule-Thomson effect) and / or heat production (for example for heating rectification columns) are returned to the separation device 20.
  • the CO circulation stream can be wholly or partially expanded in the connected CO expander 80, In the event that plant 1 is operated with a feed stream E ", which is a conventional synthesis gas E, the H 2 -rich gas fraction G is removed from the separator 20 withdrawn and (via the line 22) in a
  • Pressure swing adsorption 30 initiated. Therein, the gas fraction G is passed under pressure into (at least) an adsorber which adsorbs especially CO, but also CH4, C0 2, H 2 0 and inert gases, wherein the thus formed H 2 product stream P via a line 33 from the pressure swing adsorption system 30 is withdrawn and is available for further processing outside the plant boundary (AG).
  • an adsorber which adsorbs especially CO, but also CH4, C0 2, H 2 0 and inert gases
  • This gas is withdrawn as flushing gas S from the DWA 30 and fed via a line 31 to a compressor 40 with two sections 41, 42.
  • the purge gas S passes through both sections 41 and 42 of the compressor 40, wherein each section 41, 42 may consist of several stages.
  • the flash gas F from the separator 20 is supplied via a line 29 of the second compressor section 42 of the (recirculation) compressor 40 and withdrawn together with the purge gas S as the recycle stream R from the two-stage compressor 40.
  • the recycle stream R is then further cooled via a heat exchanger 50 (eg compressor aftercooler) and upstream of the adsorption stage
  • Temperature regulator 53 the temperature (actual value) of the feed stream E "in the line 200.
  • the temperature controller 53 cooperates with a controllable valve 52 of a bypass line 51, which bridges the heat exchanger 50. If the temperature (actual value) of the feed stream E" to low, it opens
  • Temperature controller 53, the valve 52 of the bypass line (bypass) 51 and a corresponding partial flow of the return flow R does not flow through the heat exchanger 50, but via the bypass line 51 and increases accordingly
  • At least one partial stream of the CO product stream P 'downstream of the compressor 28 can also be returned via the second section 42 of the compressor 40 (compare line 23, 29) to the feed stream E "as return stream R.
  • Raw carbon monoxide stream E ' is operated, the first section 41 of the compressor 40 can be turned off to save energy.
  • the invention advantageously allows the adjustment of the H 2 / CO ratio (to a certain value or within suitable limits) upstream of the separator 20, in particular independently of the composition of the feed stream E ".
  • the invention advantageously allows the use of two feed gases E, E ', which can be mixed together gradually, without the plant 1

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  • Combustion & Propulsion (AREA)
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  • Separation Of Gases By Adsorption (AREA)
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Abstract

L'invention concerne un procédé de production d'un flux de produit H2 (P) et d'un flux de produit CO (Ρ') à partir d'un flux de départ (E"), comprenant les étapes suivantes : introduction d'un flux de départ (E") contenant du H2 et du CO dans un système de séparation (20), qui est en particulier disposé dans une boîte froide ; séparation du flux de départ (E") dans ce système de séparation (20) pour donner une fraction gazeuse (G) riche en H2 contenant du CO et un condensat riche en CO contenant du H2, le condensat étant séparé pour donner un gaz de vaporisation éclair (F) riche en H2 et le flux de produit CO (Ρ'). Lorsque le rapport H2/CO du flux de départ (E") est supérieur ou égal à une valeur seuil prédéfinissable, on fait passer la fraction gazeuse (G), pour séparer le CO et d'autres composants (par ex. CH4, CO2, H2O et gaz inertes), dans au moins un adsorbant d'un système d'adsorption à pression alternée (30) de façon que ces composants soient adsorbés sur le ou lesdits adsorbants. Pour épurer l'adsorbant, on le balaye avec une partie du flux de produit H2 (P) soutirée du système d'adsorption à pression alternée (30) pour servir de gaz de balayage (S). Ce gaz de balayage (S) et le gaz de vaporisation éclair (F) sont recyclés dans le flux de départ (E") en amont du système de séparation (20). Lorsque le rapport H2/CO est inférieur à ladite valeur seuil, la fraction gazeuse (G), le gaz de vaporisation éclair (F) et si nécessaire une partie au moins du flux de produit CO (Ρ') sont recyclés dans le flux de départ (E") en amont du système de séparation (20). L'invention concerne en outre une installation de production d'un flux de produit H2 (P) et d'un flux de produit CO (Ρ').
EP13734667.2A 2012-07-17 2013-07-04 PROCÉDÉ ET INSTALLATION DE PRODUCTION D'UN FLUX DE PRODUIT H2 ET D'UN FLUX DE PRODUIT CO& xA; Withdrawn EP2906502A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012014094.0A DE102012014094A1 (de) 2012-07-17 2012-07-17 Verfahren und Anlage zur Erzeugung eines H2-Produktstromes und eines CO-Produktstromes
PCT/EP2013/001972 WO2014012629A2 (fr) 2012-07-17 2013-07-04 Procédé et installation de production d'un flux de produit h2 et d'un flux de produit co

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EP2906502A2 true EP2906502A2 (fr) 2015-08-19

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CN (1) CN104956171A (fr)
DE (1) DE102012014094A1 (fr)
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WO (1) WO2014012629A2 (fr)

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CN111065716A (zh) 2017-09-29 2020-04-24 研究三角协会 用于产生氢气的方法和设备
KR20230133946A (ko) 2017-09-29 2023-09-19 리써치 트라이앵글 인스티튜트 하이드로카본 공급물로부터 합성 가스를 생산하기 위한 화학 반응기로서의 내연 기관
CN108128754A (zh) * 2017-12-28 2018-06-08 上海华林工业气体有限公司 一种易于判断HyCO冷箱是否堵塞的系统与方法
US10562769B1 (en) * 2018-09-06 2020-02-18 Air Products And Chemicals, Inc. Dual product H2 and CO production with CO turndown
DE102018007868A1 (de) * 2018-10-05 2020-04-09 Linde Aktiengesellschaft Verfahren und Vorrichtung zur Erzeugung von Gasprodukten unter Verwendung eines Shift-Konventers
WO2020237563A1 (fr) * 2019-05-30 2020-12-03 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procédé et appareil de séparation de deux flux gazeux contenant chacun du monoxyde de carbone, de l'hydrogène et au moins un gaz acide
CN110902653A (zh) * 2019-12-28 2020-03-24 上海华林工业气体有限公司 合成气分离装置不停车将原料粗co切换成合成气的方法
CN111137894A (zh) * 2020-01-22 2020-05-12 上海华林工业气体有限公司 一种降低合成气分离装置最小操作区间的工艺方法与系统
CN112178457B (zh) * 2020-10-29 2024-06-11 中国石油天然气集团有限公司 一种油田低压闪蒸气管道停输积液控制系统与方法
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RU2015105188A (ru) 2016-09-10
CN104956171A (zh) 2015-09-30

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