WO2020237564A1 - Process and apparatus for the separation of a mixture of carbon monoxide, hydrogen and at least one acid gas - Google Patents

Process and apparatus for the separation of a mixture of carbon monoxide, hydrogen and at least one acid gas Download PDF

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Publication number
WO2020237564A1
WO2020237564A1 PCT/CN2019/089247 CN2019089247W WO2020237564A1 WO 2020237564 A1 WO2020237564 A1 WO 2020237564A1 CN 2019089247 W CN2019089247 W CN 2019089247W WO 2020237564 A1 WO2020237564 A1 WO 2020237564A1
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hydrogen
stream
carbon monoxide
swing adsorption
unit
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PCT/CN2019/089247
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French (fr)
Inventor
Antoine Hernandez
Wei Guan
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L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude
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Application filed by L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude filed Critical L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude
Priority to PCT/CN2019/089247 priority Critical patent/WO2020237564A1/en
Priority to CN201980096955.2A priority patent/CN113891850B/en
Publication of WO2020237564A1 publication Critical patent/WO2020237564A1/en

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    • 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
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
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    • 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
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    • 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
    • C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/40—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
    • F25J3/0204—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
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    • 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
    • C01B2203/0415—Purification by absorption in liquids
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    • 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
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    • 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
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    • 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
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • 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
    • C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
    • 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
    • C01B2203/145—At least two purification steps in parallel
    • 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
    • F25J2205/40—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
    • F25J2205/64—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 by pressure-swing adsorption [PSA] at the hot 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
    • 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
    • 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

Definitions

  • the present invention relates to a process and to an apparatus for separating a mixture of hydrogen, carbon monoxide and at least one acid gas.
  • the units for producing carbon monoxide and hydrogen may involve two parts:
  • FEP front end purification
  • a unit for cryogenic separation referred to as a cold box, for the production of CO.
  • PSA unit for the production of H2.
  • the cold box process used is a methane wash; the remaining CO content in the separated H2 rich gas stream is so low that PSA offgas recycle is not required. PSA offgas will then be used as fuel.
  • the CO content in the H2 rich gas is in this case quite high.
  • the CO is recovered using PSA offgas recycle in order to increase the economics of the project.
  • CN105948046 discloses a method for simultaneously preparing pure hydrogen and pure carbon monoxide by gasification without desorbed gas circulation.
  • the synthesis gas prepared by the gasification unit is divided into two parts, one part is used for preparing pure carbon monoxide, and the other part is used to prepare pure hydrogen.
  • one part prepares pure carbon monoxide with the crude synthesis gas prepared by gasification by a heat recovery unit, a low temperature methanol washing unit, and a cryogenic separation unit,
  • the feedstock for preparing hydrogen is divided into two parts:
  • the converted gas which is purified by a shift conversion unit and a low temperature methanol washing II unit with the crude synthesis gas prepared by gasification and contains carbon monoxide,
  • the other part is the hydrogen rich gas from a TSA device of the cryogenic separation unit, and the two parts of the gas are mixed and sent into the PSA-H2 unit to prepare pure hydrogen.
  • the method has the disadvantage of using two PSA units, which increases the overall costs.
  • the invention permits carbon monoxide and hydrogen to be produced using only one pressure swing adsorption unit. This is the preferred solution to reduce total investment compare to a two PSA solution.
  • the single PSA is fed by H2 rich gas from the cold box as well as pure shifted synthesis gas from acid gas removal absorber.
  • PSA offgas can be sent from the PSA to the inlet of the acid gas removal absorber treating the unshifted gas.
  • the disadvantage of this solution is the increase in investment of unshifted gas absorber cost and increase in operating cost due to increase in refrigerant needs to cool down the recycle gas.
  • An object of the invention is to reduce the investment in the CO2 removal absorption unit and/or operating costs.
  • a first gaseous stream containing at least carbon monoxide, hydrogen and at least one acid gas is purified in a first acid gas removal absorber to remove at least one acid gas, purified in a first temperature swing adsorption unit to remove at least carbon dioxide and then separated at a cryogenic temperature in a separation unit to produce a stream of fluid enriched in carbon monoxide, a stream of fluid enriched in hydrogen and a stream containing carbon monoxide, hydrogen and possibly methane,
  • a second gaseous stream containing at least carbon monoxide, hydrogen and at least one acid gas is sent to a shift reaction unit in which carbon monoxide and water vapour in the second stream are converted to carbon dioxide and hydrogen, the shifted second stream is purified in a second acid gas removal absorber to remove carbon dioxide and the purified second stream is sent as a feed stream to a pressure swing adsorption unit to produce a hydrogen enriched stream richer in hydrogen that the feed stream and an offgas less rich in hydrogen than the feed stream, the offgas containing carbon dioxide and methanol, and
  • the offgas and/or the stream containing carbon monoxide, hydrogen and possibly methane is/are purified to remove carbon dioxide and methanol in a unit other than the first acid gas removal absorber and the gas produced with a reduced carbon dioxide and methanol content is then sent to the inlet of the separation unit.
  • the gas produced with a reduced carbon dioxide and methanol content is then sent to the inlet of the separation unit as a feed gas to be separated.
  • the offgas and/or the stream containing carbon monoxide, hydrogen and possibly methane is/are purified to remove carbon dioxide and methanol in a second temperature swing adsorption unit, preferably only in the second temperature swing adsorption unit.
  • the offgas and/or the stream containing carbon monoxide, hydrogen and possibly methane is/are compressed upstream of the second temperature swing adsorption unit.
  • the offgas is mixed with the stream of fluid containing hydrogen and carbon monoxide from the separation unit and sent to the second temperature swing adsorption unit.
  • the stream of fluid containing carbon monoxide and hydrogen is compressed upstream of the second temperature swing adsorption unit.
  • the offgas is compressed in a first stage of the compressor and the stream of fluid containing carbon monoxide and hydrogen and the offgas are compressed in at least one subsequent stage of the compressor.
  • the stream of fluid containing carbon monoxide and hydrogen contains methane.
  • the gas purified from carbon dioxide and methanol in the second temperature swing adsorption unit is sent to the separation unit without any further step to remove carbon dioxide or methanol.
  • the first and second streams may have the same composition or different compositions
  • - a stream may be divided to form the first and second streams.
  • an apparatus for separating first and second gaseous streams each containing at least one acid gas, carbon monoxide and hydrogen to remove carbon monoxide and hydrogen comprising:
  • a first acid gas removal absorber a first temperature swing adsorption unit, a separation unit, means for sending a first gaseous stream containing at least carbon monoxide, hydrogen and at least one acid gas to be purified in the first acid gas removal absorber to remove at least one acid gas, means to send gas purified in the first acid gas removal absorber to be purified in the first temperature swing adsorption unit to remove at least carbon dioxide and means to send gas purified in at least carbon dioxide from the first temperature swing adsorption unit to be separated at a cryogenic temperature in the separation unit to produce a stream of fluid enriched in carbon monoxide, a stream of fluid enriched in hydrogen and a stream of fluid containing carbon monoxide, hydrogen and possibly methane,
  • a shift reaction unit a shift reaction unit, a second acid gas removal absorber, a pressure swing adsorption unit, means for sending a second gaseous stream containing at least carbon monoxide, hydrogen and at least one acid gas is sent to the shift reaction unit in which carbon monoxide and water vapour in the second stream are converted to carbon dioxide and hydrogen, means for sending the shifted second stream to be purified in the second acid gas removal absorber to remove carbon dioxide and means for sending the purified second stream as a feed stream to the pressure swing adsorption unit to produce a hydrogen enriched stream richer in hydrogen that the feed stream and an offgas,
  • Optional optional features include:
  • a second temperature swing adsorption unit means for sending the offgas reduced in hydrogen produced by the pressure swing adsorption unit and/or the stream of fluid containing carbon monoxide, hydrogen and possibly methane to the second temperature swing adsorption unit where it is purified to remove carbon dioxide and means for sending the purified gas from the second temperature swing adsorption unit as a feed gas to the separation unit.
  • FIGS 1 and 2 show the process according to the invention in block diagram form.
  • a mixture 3 of carbon monoxide, hydrogen and at least one acid gas, such as carbon dioxide and/or hydrogen sulphide is generated by a generator 1, for example by gasification, steam methane reforming or partial oxidation.
  • the mixture generated is divided into a first fraction 5 and a second fraction 7.
  • the mixture 3 may contain other gases, such as water, nitrogen, argon, methane, carbonyl sulphide or other hydrocarbons.
  • the mixture contains at least 10%mol hydrogen and at least 10%mol carbon monoxide.
  • the mixture may for example contain 30 to 40 %mol hydrogen and 40 to 50%carbon monoxide.
  • the two fractions could potentially have different compositions and originate from different generators.
  • the first fraction 5 is sent in gaseous form to a first acid gas removal unit AGR1A where it is separated by an absorption process operating at a low temperature, for example using the Rectisol process.
  • Absorber AGR1 A and reabsorber and stripper AGR1 R form part of the same absorption unit.
  • At least one acid gas such as carbon dioxide and/or hydrogen sulphide and/or carbonyl sulphide is removed from AGR1 R and the purified first fraction 5 with a reduced acid gas content is sent to a first temperature swing adsorption unit TSA1. In this unit, any remaining carbon dioxide and methanol are removed and the purified stream 13 produced by the adsorption is sent to a cold box CB.
  • the stream 13 is cooled, first in the first acid gas removal unit AGR1A and then in a heat exchanger within the cold box.
  • the stream 13 is separated by distillation and/or scrubbing at a cryogenic temperature, for example using any of the following: partial condensation, distillation, a methane wash tower, a carbon monoxide wash tower, where fraction 5 contains methane, a nitrogen removal column where fraction 5 contains nitrogen.
  • the cold box produces a pure carbon monoxide product stream 33, a hydrogen stream 11 and a flash gas stream FG 31 contains carbon monoxide, hydrogen and possibly methane.
  • the flash gas FG 31 may for example contain 70 to 80%mol hydrogen and 20 to 30%carbon monoxide.
  • the second fraction 7 is sent to a shift unit 14 in which carbon monoxide and water vapour in the second fraction are converted to carbon dioxide and hydrogen.
  • the shifted second fraction 15 is purified in an absorption unit AGR2A for example of the Rectisol type to remove carbon dioxide and/or hydrogen sulphide and/or carbonyl sulphide.
  • the purified second fraction 17, 19 is sent from AGR2A as a feed stream to a pressure swing adsorption unit PSA to produce a hydrogen enriched stream 21 richer in hydrogen that the feed stream 19 .
  • Absorber AGR2 A and reabsorber and stripper AGR2 R form part of the same absorption unit
  • the purified second fraction is mixed with hydrogen rich gas 11 from the cold box CB.
  • This hydrogen rich gas may have been used to regenerate the first temperature swing adsorption unit TSA1 and thus contains carbon dioxide adsorbed by the adsorption process.
  • the offgas 23 from the pressure swing adsorption unit PSA contains less hydrogen than streams 11, 19 and is optionally compressed in a compressor 25 before being sent to a second temperature swing adsorption unit TSA2.
  • a second temperature swing adsorption unit Within the second temperature swing adsorption unit, carbon dioxide and methanol in the feed stream 23 are removed and the purified stream 27 is sent as a feed stream to the cold box CB.
  • the second temperature swing adsorption unit TSA2 is regenerated using a low pressure gaseous nitrogen stream LPN2 which may come from a nearby air separation unit.
  • the nitrogen which has been used for the regeneration 29 contains carbon dioxide and methanol and is sent as stream 29 to the absorption unit AGR2.
  • the nitrogen 29 is preferably sent to a nitrogen stripping column, also known as a reabsorber AGR2R and this reduces the overall nitrogen demand of the unit.
  • a nitrogen stripping column also known as a reabsorber AGR2R and this reduces the overall nitrogen demand of the unit.
  • the optional compressor 25 may also be used to increase the pressure of the flash gas 31 from the cold box CB, thus mixing gas 31 with the PSA offgas 23 at an intermediate point of the compressor 25.
  • Either offgas 23 or gas 31 may be sent to be separated in TSA2. It is not necessary to send both streams.
  • Stream 27 is separated within the separation unit CB to improve the product yield.
  • Figure 2 shows a more detailed version of part of Figure 1.
  • Figure 2 shows the warming process for the purified mixture 13 from TSA1 in heat exchanger 14 forming part of the absorption unit AGR1.
  • Figure 2 shows that the nitrogen 29 having been used for the regeneration of second temperature swing adsorption unit TSA2 is compressed and then mixed with nitrogen stream 30.
  • the gaseous nitrogen 29 will also contain methanol and/or carbon dioxide from the second temperature swing adsorption unit TSA2.
  • the combined stream is then used in AGR2 R. in a stripping process.
  • the nitrogen may or may not need to be compressed upstream of the stripper.
  • Absorber AGR2 A and reabsorber and stripper AGR2 R form part of the same absorption unit, serving to remove carbonyl sulphide and/or hydrogen sulphide and/or carbon dioxide from gas 15 which contains at least one of these components.
  • the absorber AGR2 all undesired gas components are eliminated from gas 15 stage to produce gas 19 having a reduced carbon dioxide and/or carbonyl sulphide and/or hydrogen sulphide content.
  • Impurity-laden methanol used for the absorption is transferred from the absorber to flashing stages where the hydrogen and carbon monoxide are expelled. The hydrogen and carbon monoxide gases are then recycled to the gas 15.
  • a second flashing operation is performed in unit AGR2 R, to regenerate the methanol.
  • the reabsorber removes the sulphur components from the carbon dioxide gas.
  • Nitrogen gas 30 is used for stripping in unit AGR2 R together with nitrogen 29 which has been to regenerate the second temperature swing adsorption unit.
  • reabsorber and stripper AGR1 R and reabsorber and stripper AGR2 R may in fact be a single reabsorbed and stripper shared between absorbers AGR1 A and AGR2 A.

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Abstract

A process for separating first and second gaseous streams each containing at least one acid gas, carbon monoxide and hydrogen to remove carbon monoxide and hydrogen, a first gaseous stream (5) is purified in a first acid gas removal absorber (AGR1A), purified in a first TSA unit (TSA1) to remove at least carbon dioxide and then separated at a cryogenic temperature in a separation unit (CB) to produce a stream of fluid enriched in carbon monoxide (33), a second gaseous stream (7) is sent to a shift reaction unit (14), the shifted second stream is purified in a second acid gas removal absorber (AGR2A) to remove carbon dioxide and the purified second stream is sent as a feed stream to a PSA unit (PSA), the offgas containing carbon dioxide and methanol and the offgas and/or the stream containing carbon monoxide, hydrogen and possibly methane is/are purified to remove carbon dioxide and methanol in a second temperature swing adsorption unit (TSA2) and the gas produced with a reduced carbon dioxide and methanol content is then sent to the inlet of the separation unit (CB).

Description

PROCESS AND APPARATUS FOR THE SEPARATION OF A MIXTURE OF CARBON MONOXIDE, HYDROGEN AND AT LEAST ONE ACID GAS
The present invention relates to a process and to an apparatus for separating a mixture of hydrogen, carbon monoxide and at least one acid gas.
The units for producing carbon monoxide and hydrogen may involve two parts:
· Generation of the synthesis gas (amixture essentially containing H 2, CO, and possibly at least one of CH 4, CO 2, Ar and N 2) . Among the various industrial synthesis gas production processes, that based on coal gasification is becoming more and more widespread especially in countries that are rich in coal deposits such as China. The process of partial oxidation of natural gas may also prove advantageous for the production of CO alone or with low H 2/CO production ratios. Another process is steam reforming.
· Purification of the synthesis gas. This includes the following:
- a scrubbing unit using a liquid solvent to remove most of the acid gases contained in the synthesis gas;
- a front end purification (FEP) unit for purification over adsorbent beds in order to remove impurities that would freeze under cryogenic temperatures;
- a unit for cryogenic separation, referred to as a cold box, for the production of CO.
- a unit for purification over adsorbent beds referred to as a PSA unit for the production of H2.
When the ratio between the H2 product flow and the CO product flow required by downstream consumers is higher than the ratio in the synthesis gas directly produced by the synthesis gas generation, then a shift reactor can be added, fed by part of the synthesis gas generated. The remaining synthesis gas which does not feed the shift reactor is sent to the FEP upstream of the cryogenic section or “cold box” for CO production.
When the synthesis gas is produced by a steam methane reformer, the cold box process used is a methane wash; the remaining CO content in the separated H2 rich gas stream is so low that PSA offgas recycle is not required. PSA offgas will then be used as fuel.
When synthesis gas is produced by slurry coal gasification or partial oxidation, then the cold box process used is partial condensation.
The CO content in the H2 rich gas is in this case quite high. In this case, the CO is recovered using PSA offgas recycle in order to increase the economics of the project.
CN105948046 discloses a method for simultaneously preparing pure hydrogen and pure carbon monoxide by gasification without desorbed gas circulation. The synthesis gas prepared by the gasification unit is divided into two parts, one part is used for preparing pure carbon monoxide, and the other part is used to prepare pure hydrogen.
The process of preparing pure carbon monoxide is divided into two parts:
- one part prepares pure carbon monoxide with the crude synthesis gas prepared by gasification by a heat recovery unit, a low temperature methanol washing unit, and a cryogenic separation unit,
- and the other part is used for preparing pure carbon monoxide by sending the hydrogen rich gas from the outlet of the cold box of the cryogenic separation unit into a PSA-CO unit.
The feedstock for preparing hydrogen is divided into two parts:
- one part is the converted gas which is purified by a shift conversion unit and a low temperature methanol washing II unit with the crude synthesis gas prepared by gasification and contains carbon monoxide,
- and the other part is the hydrogen rich gas from a TSA device of the cryogenic separation unit, and the two parts of the gas are mixed and sent into the PSA-H2 unit to prepare pure hydrogen.
The method has the disadvantage of using two PSA units, which increases the overall costs.
Another possible scheme where one single PSA is used is when CO is produced together with H2 and synthesis gas for MeOH synthesis. The disadvantage of this solution is that it requires MeOH synthesis investment and so depends on the MeOH market demands.
The invention permits carbon monoxide and hydrogen to be produced using only one pressure swing adsorption unit. This is the preferred solution to reduce total investment compare to a two PSA solution.
The single PSA is fed by H2 rich gas from the cold box as well as pure shifted synthesis gas from acid gas removal absorber. PSA offgas can be sent from the PSA to the inlet of the acid gas removal absorber treating the unshifted gas. The disadvantage of this solution is the increase in investment of unshifted gas absorber cost and increase in operating cost due to increase in refrigerant needs to cool down the recycle gas.
An object of the invention is to reduce the investment in the CO2 removal absorption unit and/or operating costs.
According to an object of the invention, there is provided a process for separating first and second gaseous streams, each containing at least one acid gas, carbon monoxide and hydrogen to remove carbon monoxide and hydrogen in which:
i) A first gaseous stream containing at least carbon monoxide, hydrogen and at least one acid gas is purified in a first acid gas removal absorber to remove at least one acid gas, purified in a first temperature swing adsorption unit to remove at least carbon dioxide and then separated at a cryogenic temperature in a separation unit to produce a stream of fluid enriched in carbon monoxide, a stream of fluid enriched in hydrogen and a stream containing carbon monoxide, hydrogen and possibly methane,
ii) A second gaseous stream containing at least carbon monoxide, hydrogen and at least one acid gas is sent to a shift reaction unit in which carbon monoxide and water vapour in the second stream are converted to carbon dioxide and hydrogen, the shifted second stream is purified in a second acid gas removal absorber to remove carbon dioxide and the purified second stream is sent as a feed stream to a pressure swing adsorption unit to produce a hydrogen enriched stream richer in hydrogen that the feed stream and an offgas less rich in hydrogen than the feed stream, the offgas containing carbon dioxide and methanol, and
iii) The offgas and/or the stream containing carbon monoxide, hydrogen and possibly methane is/are purified to remove carbon dioxide and methanol in a unit other than the first acid gas removal absorber and the gas produced with a reduced carbon dioxide and methanol content is then sent to the inlet of the separation unit.
According to other optional aspects:
- the gas produced with a reduced carbon dioxide and methanol content is then sent to the inlet of the separation unit as a feed gas to be separated.
- the offgas and/or the stream containing carbon monoxide, hydrogen and possibly methane is/are purified to remove carbon dioxide and methanol in a second temperature swing adsorption unit, preferably only in the second temperature swing adsorption unit.
- the offgas and/or the stream containing carbon monoxide, hydrogen and possibly methane is/are compressed upstream of the second temperature swing adsorption unit.
- the offgas is mixed with the stream of fluid containing hydrogen and carbon monoxide from the separation unit and sent to the second temperature swing adsorption unit.
- the stream of fluid containing carbon monoxide and hydrogen is compressed upstream of the second temperature swing adsorption unit.
- the stream of fluid containing carbon monoxide and hydrogen and the offgas are compressed in the same compressor.
- the offgas is compressed in a first stage of the compressor and the stream of fluid containing carbon monoxide and hydrogen and the offgas are compressed in at least one subsequent stage of the compressor.
- the stream of fluid containing carbon monoxide and hydrogen contains methane.
- the gas purified from carbon dioxide and methanol in the second temperature swing adsorption unit is sent to the separation unit without any further step to remove carbon dioxide or methanol.
- the first and second streams may have the same composition or different compositions
- a stream may be divided to form the first and second streams.
According to another aspect of the invention, there is provided an apparatus for separating first and second gaseous streams each containing at least one acid gas, carbon monoxide and hydrogen to remove carbon monoxide and hydrogen comprising:
- a first acid gas removal absorber, a first temperature swing adsorption unit, a separation unit, means for sending a first gaseous stream containing at least carbon monoxide, hydrogen and at least one acid gas to be purified in the first acid gas removal absorber to remove at least one acid gas, means to send gas purified in the first acid gas removal absorber to be purified in the first temperature swing  adsorption unit to remove at least carbon dioxide and means to send gas purified in at least carbon dioxide from the first temperature swing adsorption unit to be separated at a cryogenic temperature in the separation unit to produce a stream of fluid enriched in carbon monoxide, a stream of fluid enriched in hydrogen and a stream of fluid containing carbon monoxide, hydrogen and possibly methane,
- a shift reaction unit, a second acid gas removal absorber, a pressure swing adsorption unit, means for sending a second gaseous stream containing at least carbon monoxide, hydrogen and at least one acid gas is sent to the shift reaction unit in which carbon monoxide and water vapour in the second stream are converted to carbon dioxide and hydrogen, means for sending the shifted second stream to be purified in the second acid gas removal absorber to remove carbon dioxide and means for sending the purified second stream as a feed stream to the pressure swing adsorption unit to produce a hydrogen enriched stream richer in hydrogen that the feed stream and an offgas,
- and means for sending the offgas and/or the stream containing carbon monoxide, hydrogen and possibly methane to a unit other than the first acid gas removal absorber to be purified to remove carbon dioxide and methanol and means for sending the gas produced with a reduced carbon dioxide and methanol content is to the inlet of the separation unit.
Optional optional features include:
- means for sending at least part of the at least part of the stream enriched in hydrogen from the separation unit as a feed stream to the pressure swing adsorption unit; following use to regenerate the first temperature swing adsorption unit.
- a second temperature swing adsorption unit, means for sending the offgas reduced in hydrogen produced by the pressure swing adsorption unit and/or the stream of fluid containing carbon monoxide, hydrogen and possibly methane to the second temperature swing adsorption unit where it is purified to remove carbon dioxide and means for sending the purified gas from the second temperature swing adsorption unit as a feed gas to the separation unit.
- nitrogen gas from an external source is used to regenerate the second temperature adsorption unit and the nitrogen gas which has been used for the regeneration is sent to a reabsorber forming part of the same absorption unit as the second acid gas removal absorber.
-a compressor and means for sending the gas reduced in hydrogen produced by the pressure swing adsorption unit, to be compressed by the compressor upstream of the second temperature swing adsorption unit.
- means for sending the gas containing hydrogen, carbon monoxide and possibly methane produced by the separation unit as a feed stream to the second temperature swing adsorption unit to be separated.
The invention will now be described in detail, making reference to the figures.
Figures 1 and 2 show the process according to the invention in block diagram form.
In Figure 1, a mixture 3 of carbon monoxide, hydrogen and at least one acid gas, such as carbon dioxide and/or hydrogen sulphide is generated by a generator 1, for example by gasification, steam methane reforming or partial oxidation. The mixture generated is divided into a first fraction 5 and a second fraction 7. The mixture 3 may contain other gases, such as water, nitrogen, argon, methane, carbonyl sulphide or other hydrocarbons. The mixture contains at least 10%mol hydrogen and at least 10%mol carbon monoxide. The mixture may for example contain 30 to 40 %mol hydrogen and 40 to 50%carbon monoxide.
The two fractions could potentially have different compositions and originate from different generators.
The first fraction 5 is sent in gaseous form to a first acid gas removal unit AGR1A where it is separated by an absorption process operating at a low temperature, for example using the Rectisol
Figure PCTCN2019089247-appb-000001
process. Absorber AGR1 A and reabsorber and stripper AGR1 R form part of the same absorption unit. At least one acid gas such as carbon dioxide and/or hydrogen sulphide and/or carbonyl sulphide is removed from AGR1 R and the purified first fraction 5 with a reduced acid gas content is sent to a first temperature swing adsorption unit TSA1. In this unit, any remaining carbon dioxide and methanol are removed and the purified stream 13 produced by the adsorption is sent to a cold box CB.
Upstream of the cold box CB, the stream 13 is cooled, first in the first acid gas removal unit AGR1A and then in a heat exchanger within the cold box. Within the cold box, the stream 13 is separated by distillation and/or scrubbing at a cryogenic temperature, for example using any of the following: partial condensation, distillation, a methane wash tower, a carbon monoxide wash tower, where fraction 5 contains methane, a nitrogen removal column where fraction 5 contains nitrogen.
The cold box produces a pure carbon monoxide product stream 33, a hydrogen stream 11 and a flash gas stream FG 31 contains carbon monoxide, hydrogen and possibly methane. The flash gas FG 31 may for example contain 70 to 80%mol hydrogen and 20 to 30%carbon monoxide.
The second fraction 7 is sent to a shift unit 14 in which carbon monoxide and water vapour in the second fraction are converted to carbon dioxide and hydrogen. The shifted second fraction 15 is purified in an absorption unit AGR2A for example of the Rectisol
Figure PCTCN2019089247-appb-000002
type to remove carbon dioxide and/or hydrogen sulphide and/or carbonyl sulphide. The purified second fraction 17, 19 is sent from AGR2A as a feed stream to a pressure swing adsorption unit PSA to produce a hydrogen enriched stream 21 richer in hydrogen that the feed stream 19 . Absorber AGR2 A and reabsorber and stripper AGR2 R form part of the same absorption unit
Upstream of the pressure swing adsorption unit PSA, the purified second fraction is mixed with hydrogen rich gas 11 from the cold box CB. This hydrogen rich gas may have been used to regenerate the first temperature swing adsorption unit TSA1 and thus contains carbon dioxide adsorbed by the adsorption process.
The offgas 23 from the pressure swing adsorption unit PSA contains less hydrogen than  streams  11, 19 and is optionally compressed in a compressor 25 before being sent to a second temperature swing adsorption unit TSA2. Within the second temperature swing adsorption unit, carbon dioxide and methanol in the feed stream 23 are removed and the purified stream 27 is sent as a feed stream to the cold box CB.
The second temperature swing adsorption unit TSA2 is regenerated using a low pressure gaseous nitrogen stream LPN2 which may come from a nearby air separation unit. The nitrogen which has been used for the regeneration 29 contains carbon dioxide and methanol and is sent as stream 29 to the absorption unit AGR2.
The nitrogen 29 is preferably sent to a nitrogen stripping column, also known as a reabsorber AGR2R and this reduces the overall nitrogen demand of the unit.
The optional compressor 25 may also be used to increase the pressure of the flash gas 31 from the cold box CB, thus mixing gas 31 with the PSA offgas 23 at an intermediate point of the compressor 25.
Either offgas 23 or gas 31 may be sent to be separated in TSA2. It is not necessary to send both streams.
Stream 27 is separated within the separation unit CB to improve the product yield.
Figure 2 shows a more detailed version of part of Figure 1. In addition to the features already explained above, Figure 2 shows the warming process for the purified mixture 13 from TSA1 in heat exchanger 14 forming part of the absorption unit AGR1.
In addition, Figure 2 shows that the nitrogen 29 having been used for the regeneration of second temperature swing adsorption unit TSA2 is compressed and then mixed with nitrogen stream 30. The gaseous nitrogen 29 will also contain methanol and/or carbon dioxide from the second temperature swing adsorption unit TSA2. The combined stream is then used in AGR2 R. in a stripping process. The nitrogen may or may not need to be compressed upstream of the stripper.
Absorber AGR2 A and reabsorber and stripper AGR2 R form part of the same absorption unit, serving to remove carbonyl sulphide and/or hydrogen sulphide and/or carbon dioxide from gas 15 which contains at least one of these components. In the absorber AGR2, all undesired gas components are eliminated from gas 15 stage to produce gas 19 having a reduced carbon dioxide and/or carbonyl sulphide and/or hydrogen sulphide content. Impurity-laden methanol used for the absorption is transferred from the absorber to flashing stages where the hydrogen and carbon monoxide are expelled. The hydrogen and carbon monoxide gases are then recycled to the gas 15. A second flashing operation is performed in unit AGR2 R, to regenerate the methanol. The reabsorber removes the sulphur components from the carbon dioxide gas. Nitrogen gas 30 is used for stripping in unit AGR2 R together with nitrogen 29 which has been to regenerate the second temperature swing adsorption unit.
It is possible that reabsorber and stripper AGR1 R and reabsorber and stripper AGR2 R may in fact be a single reabsorbed and stripper shared between absorbers AGR1 A and AGR2 A.
A typical Rectisol
Figure PCTCN2019089247-appb-000003
process is described in Gas Purification, 1997, fifth edition, page 1222.

Claims (15)

  1. Process for separating first and second gaseous streams each containing at least one acid gas, carbon monoxide and hydrogen to remove carbon monoxide and hydrogen in which:
    i) A first gaseous stream (5) containing at least carbon monoxide, hydrogen and at least one acid gas is purified in a first acid gas removal absorber (AGR1A) to remove at least one acid gas, purified in a first temperature swing adsorption unit (TSA1) to remove at least carbon dioxide and then separated at a cryogenic temperature in a separation unit (CB) to produce a stream of fluid enriched in carbon monoxide (33) , a stream of fluid enriched in hydrogen (11) and a stream containing carbon monoxide, hydrogen and possibly methane (FG, 31) ,
    ii) A second gaseous stream (7) containing at least carbon monoxide, hydrogen and at least one acid gas is sent to a shift reaction unit (14) in which carbon monoxide and water vapour in the second stream are converted to carbon dioxide and hydrogen, the shifted second stream is purified in a second acid gas removal absorber (AGR2A) to remove carbon dioxide and the purified second stream is sent as a feed stream to a pressure swing adsorption unit (PSA) to produce a hydrogen enriched stream (21) richer in hydrogen that the feed stream and an offgas (23) less rich in hydrogen than the feed stream, the offgas containing carbon dioxide and methanol, and
    iii) The offgas and/or the stream containing carbon monoxide, hydrogen and possibly methane is/are purified to remove carbon dioxide and methanol in a unit (TSA2) other than the first acid gas removal absorber and the gas produced with a reduced carbon dioxide and methanol content is then sent to the inlet of the separation unit (CB) .
  2. Process according to Claim 1 wherein the offgas (23) and/or the stream containing carbon monoxide, hydrogen and possibly methane (31, FG) is/are purified to remove carbon dioxide and methanol in a second temperature swing adsorption unit (TSA2) , preferably only in the second temperature swing adsorption unit.
  3. Process according to Claim 1 or 2 wherein the offgas (23) and/or the stream containing carbon monoxide, hydrogen and possibly methane (31, FG) is/are compressed upstream of the second temperature swing adsorption unit (TSA2) .
  4. Process according to Claim 1, 2 or 3 wherein the offgas (23) is mixed with the stream of fluid containing hydrogen and carbon monoxide (31, FG) from the separation unit (CB) and sent to the second temperature swing adsorption unit (TSA2) .
  5. Process according to Claim 4 wherein the stream of fluid containing carbon monoxide and hydrogen (31, FG) is compressed upstream of the second temperature swing adsorption unit (TSA2) .
  6. Process according to Claims 3 and 5 wherein the stream of fluid containing carbon monoxide and hydrogen (31) and the offgas (23) are compressed in the same compressor (25) .
  7. Process according to Claim 6 wherein the offgas (23) is compressed in a first stage of the compressor (25) and the stream of fluid containing carbon monoxide and hydrogen (31) and the offgas are compressed in at least one subsequent stage of the compressor.
  8. Process according to any preceding claim wherein the stream of fluid containing carbon monoxide and hydrogen (31) contains methane.
  9. Process according to any preceding claim wherein the gas purified from carbon dioxide and methanol in the second temperature swing adsorption unit (TSA2) is sent to the separation unit (CB) without any further step to remove carbon dioxide or methanol.
  10. Apparatus for separating first and second gaseous streams (5, 7) each containing at least one acid gas, carbon monoxide and hydrogen to remove carbon monoxide and hydrogen comprising:
    - a first acid gas removal absorber (AGR1A) , a first temperature swing adsorption unit (TSA1) , a separation unit (CB) , means for sending a first gaseous stream (5) containing at least carbon monoxide, hydrogen and at least one acid gas to be purified in the first acid gas removal absorber to remove at least one acid gas, means to send gas (9) purified in the first acid gas removal absorber to be purified in the first temperature swing adsorption unit to remove at least carbon dioxide and means to send gas purified in at least carbon dioxide from the first temperature swing adsorption unit to be separated at a cryogenic temperature in the separation unit to produce a stream of fluid enriched in carbon monoxide (33) , a stream of fluid enriched in hydrogen (11) and a stream of fluid containing carbon monoxide, hydrogen and possibly methane (31, FG) ,
    - a shift reaction unit (14) , a second acid gas removal absorber (AGR2A) , a pressure swing adsorption unit (PSA) , means for sending a second gaseous stream (7) containing at least carbon monoxide, hydrogen and at least one acid gas is sent to the shift reaction unit in which carbon monoxide and water vapour in the second stream are converted to carbon dioxide and hydrogen, means for sending the shifted second stream (15) to be purified in the second acid gas removal absorber to remove carbon dioxide and means for sending the purified second stream (17, 19) as a feed stream to the pressure swing adsorption unit to produce a hydrogen enriched stream richer in hydrogen that the feed stream (21) and an offgas (31) ,
    - and means for sending the offgas and/or the stream containing carbon monoxide, hydrogen and possibly methane to a unit (TSA2) other than the first acid gas removal absorber to be purified to remove carbon dioxide and methanol and means for sending the gas produced (27) with a reduced carbon dioxide and methanol content is to the inlet of the separation unit (CB) .
  11. Apparatus according to Claim 10 comprising means for sending at least part of the at least part of the stream enriched in hydrogen (11) from the separation unit (CB) as a feed stream to the pressure swing adsorption unit (PSA) following use to regenerate the first temperature swing adsorption unit (TSA1) .
  12. Apparatus according to Claim 10 or 11 comprising a second temperature swing adsorption unit (TSA2) , means for sending the offgas (23) reduced in hydrogen produced by the pressure swing adsorption unit and/or the stream of fluid containing  carbon monoxide, hydrogen and possibly methane (31) to the second temperature swing adsorption unit where it is purified to remove carbon dioxide and means for sending the purified gas (27) from the second temperature swing adsorption unit as a feed gas to the separation unit (CB) .
  13. Apparatus according to Claim 12 wherein nitrogen gas (LPN2) from an external source is used to regenerate the second temperature adsorption unit (TSA2) and the nitrogen gas which has been used for the regeneration is sent to a reabsorber (AGR1 R, AGR2R) forming part of the same absorption unit as the second acid gas removal absorber.
  14. Apparatus according to Claim 13 comprising a compressor (25) and means for sending the gas reduced in hydrogen (23) produced by the pressure swing adsorption unit, to be compressed by the compressor upstream of the second temperature swing adsorption unit (TSA2) .
  15. Apparatus according to Claim 13 or 14 comprising means for sending the gas containing hydrogen, carbon monoxide and possibly methane (FG, 31) produced by the separation unit (CB) as a feed stream to the second temperature swing adsorption unit (TSA2) to be separated.
PCT/CN2019/089247 2019-05-30 2019-05-30 Process and apparatus for the separation of a mixture of carbon monoxide, hydrogen and at least one acid gas WO2020237564A1 (en)

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