FR3013106A1 - CRYOGENIC SEPARATION PROCESS FOR THE PRODUCTION OF A MIXTURE OF HYDROGEN AND NITROGEN CONTAINING LOW CO AND CH4 CONTENT - Google Patents
CRYOGENIC SEPARATION PROCESS FOR THE PRODUCTION OF A MIXTURE OF HYDROGEN AND NITROGEN CONTAINING LOW CO AND CH4 CONTENT Download PDFInfo
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- FR3013106A1 FR3013106A1 FR1361069A FR1361069A FR3013106A1 FR 3013106 A1 FR3013106 A1 FR 3013106A1 FR 1361069 A FR1361069 A FR 1361069A FR 1361069 A FR1361069 A FR 1361069A FR 3013106 A1 FR3013106 A1 FR 3013106A1
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- Prior art keywords
- hydrogen
- enriched
- liquid
- methane
- nitrogen
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000001257 hydrogen Substances 0.000 title claims abstract description 44
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 44
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 31
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 238000000926 separation method Methods 0.000 title claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 101
- 239000007788 liquid Substances 0.000 claims abstract description 56
- 239000007789 gas Substances 0.000 claims abstract description 50
- 238000005406 washing Methods 0.000 claims abstract description 30
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 23
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 23
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 12
- 239000012530 fluid Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 238000009834 vaporization Methods 0.000 claims description 2
- 230000008016 vaporization Effects 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 230000000994 depressogenic effect Effects 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000002309 gasification Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006257 total synthesis reaction Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
- F25J3/0233—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of CnHm with 1 carbon atom or more
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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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0204—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the feed stream
- F25J3/0223—H2/CO mixtures, i.e. synthesis gas; Water gas or shifted synthesis gas
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
- F25J3/0257—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 nitrogen
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
- F25J3/0276—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of H2/N2 mixtures, i.e. of ammonia synthesis gas
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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
- 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
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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
- 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
- C01B2203/048—Composition of the impurity the impurity being an organic compound
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/068—Ammonia synthesis
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- 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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2205/00—Processes or apparatus using other separation and/or other processing means
- F25J2205/30—Processes or apparatus using other separation and/or other processing means using a washing, e.g. "scrubbing" or bubble column for purification purposes
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- 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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2215/00—Processes characterised by the type or other details of the product stream
- F25J2215/02—Mixing or blending of fluids to yield a certain product
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- 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
- F25J2245/42—Processes or apparatus involving steps for recycling of process streams the recycled stream being nitrogen
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2270/00—Refrigeration techniques used
- F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
- F25J2270/904—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration by liquid or gaseous cryogen in an open loop
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Separation By Low-Temperature Treatments (AREA)
Abstract
Un appareil de séparation cryogénique par lavage à l'azote pour la production d'un mélange d'hydrogène et d'azote (29) contenant moins que 1% de CH4 et/ou moins que 1% de CO comprend un échangeur de chaleur (E2), des moyens pour envoyer un gaz de synthèse (1,3) se refroidir et se condenser partiellement, un premier pot séparateur (P1), des moyens pour envoyer le fluide partiellement condensé dans l'échangeur au premier pot pour produire un gaz enrichi en hydrogène (9) et un premier liquide (7) enrichi en méthane, des moyens (E2) pour condenser partiellement le gaz enrichi en hydrogène pour produire une vapeur enrichie en hydrogène (11) et un deuxième liquide enrichi en méthane (13), un deuxième pot séparateur (P2) pour séparer la vapeur et le deuxième liquide, une colonne de lavage (C), des moyens pour envoyer au moins une partie de la vapeur enrichie en hydrogène du deuxième pot séparateur vers la colonne de lavage, des moyens pour envoyer de l'azote liquide (15) en tête de la colonne de lavage, des moyens pour soutirer le mélange d'hydrogène et d'azote (21) en tête de la colonne de lavage, des moyens pour mélanger le premier et le deuxième liquides enrichis en méthane, des moyens (V1,V2) pour détendre les liquides à mélanger et des moyens pour envoyer au moins une partie du mélange des liquides détendus dans l'échangeur de chaleur pour former un gaz riche en méthane (35).A nitrogen washing cryogenic separation apparatus for producing a mixture of hydrogen and nitrogen (29) containing less than 1% CH4 and / or less than 1% CO comprises a heat exchanger ( E2), means for sending a synthesis gas (1,3) to cool and partially condense, a first separator pot (P1), means for sending the partially condensed fluid in the exchanger to the first pot to produce a gas hydrogen-enriched (9) and a first methane-enriched liquid (7), means (E2) for partially condensing the hydrogen-enriched gas to produce a hydrogen-enriched vapor (11) and a second methane-enriched liquid (13) , a second separator pot (P2) for separating the vapor and the second liquid, a washing column (C), means for sending at least a portion of the hydrogen-enriched vapor from the second separator pot to the washing column, means for sending liquid nitrogen (15 ) at the top of the washing column, means for withdrawing the mixture of hydrogen and nitrogen (21) at the top of the washing column, means for mixing the first and second liquids enriched in methane, means ( V1, V2) for expanding the liquids to be mixed and means for sending at least a portion of the mixture of the expanded liquids into the heat exchanger to form a methane-rich gas (35).
Description
La présente invention concerne un procédé et un appareil de séparation cryogénique pour la production d'un mélange d'hydrogène et azote contenant 5 une faible teneur en CO et une faible teneur en CH4. Le procédé permet une production combinée de CH4 sous forme gazeuse. Les unités de production d'un mélange d'hydrogène et d'azote peuvent être séparées en deux parties : - génération du gaz de synthèse (mélange contenant H2, CO, CH4, 10 CO2, Ar et N2 essentiellement). Parmi les diverses voies industrielles de production de gaz de synthèse, la gazéification de charbon est une méthode très développée ces dernières année. La conception de cette unité qui comprend un réacteur de gazéification du charbon avec de l'oxygène est basée sur la production en hydrogène requises. 15 - purification du gaz de synthèse. On retrouve : - une unité de lavage à un solvant liquide pour éliminer la plus grande partie des gaz acides contenus dans le gaz de synthèse. - une unité d'épuration sur lit d'adsorbants. - Une unité de séparation par voie cryogénique dite boite froide pour la 20 production de mélange hydrogène et azote avec un ratio défini H2/N2. Généralement le gaz de synthèse comprend un mélange à haute pression (entre 30 et 60 bar) contenant les composés suivants : H2, CO, CH4, N2, Ar. Le procédé selon l'invention permet la séparation de monoxyde de 25 carbone et de méthane quand le gaz à séparer contient moins que 5% de monoxyde de carbone. Tous les pourcentages dans ce document concernant des puretés sont des pourcentages volumiques. Pour produire d'un mélange H2/N2 contenant de très faibles teneurs en CH4 et en CO (notamment pour la production d'ammoniac), le procédé le plus 30 adapté est le procédé par lavage à l'azote. Ce procédé permet de produire un mélange H2/N2 sous pression avec une bonne pureté. Comme décrit dans US-A-4544390, le gaz de synthèse contenant entre 15 et 30% de monoxyde de carbone est refroidi. Le gaz de synthèse est séparé par une première condensation partielle, produisant un liquide riche en méthane et un gaz. Le gaz subit une condensation partielle et la vapeur produite alimente une colonne de lavage au N2 où on injecte du N2 liquide en tête de colonne, ce qui permet d'abaisser la teneur en CH4 et CO dans la vapeur produite en tête de colonne de lavage. Ainsi le gaz de tête contenant de l'hydrogène et de l'azote a des teneurs faibles en CH4 et en CO (au niveau ppm) correspondant au besoin de l'unité de production d'ammoniac. En cuve de colonne, le liquide contenant les impuretés CH4 et CO et une partie de N2 venant de lavage est détendu à faible pression et utilisé pour condenser l'azote destiné à servir de liquide de lavage. L'idée mise en avant dans cette proposition d'invention permettrait de séparer le CH4 du gaz de synthèse en amont de l'étape de lavage et ainsi d'augmenter la teneur en CH4 du fluide CH4 séparé et/ou d'augmenter le rendement de récupération en CH4.Il est prévu de valoriser le CH4 en le recyclant dans un système de production de gaz de synthèse pour augmenter la production de molécule d'H2, par exemple en l'utilisant comme gaz de charge d'un four de reformage, d'un réacteur autothermique ou d'un réacteur d'oxydation partielle. Plus la concentration de CH4 est élevée, plus l'efficacité du système global est importante. En effet, en abaissant la teneur notamment en N2 dans le fuide riche en CH4, on réduit l'investissement de l'unité de génération de gaz de synthèse à partir du fluide riche en CH4 et on consomme moins d'énergie à préchauffer le fluide riche en CH4. De même, plus le rendement de récupération de CH4 est élevé, plus la quantité d'hydrogène produite sera importante. On améliore ainsi l'efficacité globale du système de production de gaz de synthèse. Ainsi lorsque le gaz de synthèse est produit principalement par un réacteur de gazéification de charbon, la proposition d'invention permet d'augmenter la pureté et/ou le taux de récupération du CH4 résiduel contenu dans le gaz de synthèse pour augmenter la production de gaz de synthèse totale ou bien de réduire l'investissement de l'unité de gazéification. Le procédé a pour but d'augmenter la concentration de méthane et/ou le rendement de récupération de CH4 dans le gaz produit par condensation partielle, afin de réduire la teneur en CH4 dans le fluide à envoyer à la colonne de lavage.The present invention relates to a cryogenic separation method and apparatus for producing a mixture of hydrogen and nitrogen containing low CO content and low CH4 content. The process allows a combined production of CH4 in gaseous form. The units for producing a mixture of hydrogen and nitrogen can be separated into two parts: synthesis of the synthesis gas (mixture containing H2, CO, CH4, CO2, Ar and N2 essentially). Of the various synthetic gas production routes, coal gasification is a very advanced method in recent years. The design of this unit which includes a coal gasification reactor with oxygen is based on the required hydrogen production. Purification of the synthesis gas. We find: - a washing unit with a liquid solvent to remove most of the acid gases contained in the synthesis gas. an adsorbent bed purification unit. - A cryogenic separation unit called cold box for the production of hydrogen and nitrogen mixture with a defined ratio H2 / N2. Generally the synthesis gas comprises a mixture at high pressure (between 30 and 60 bar) containing the following compounds: H2, CO, CH4, N2, Ar. The process according to the invention allows the separation of carbon monoxide and methane. when the gas to be separated contains less than 5% carbon monoxide. All percentages in this document relating to purities are percentages by volume. In order to produce an H2 / N2 mixture containing very low levels of CH4 and CO (especially for the production of ammonia), the most suitable method is the nitrogen washing process. This process produces a H2 / N2 mixture under pressure with good purity. As described in US-A-4544390, synthesis gas containing between 15 and 30% carbon monoxide is cooled. The synthesis gas is separated by a first partial condensation, producing a liquid rich in methane and a gas. The gas is partially condensed and the steam produced feeds a N 2 scrubbing column where liquid N 2 is injected at the top of the column, thereby lowering the CH 4 and CO content in the steam produced at the top of the scrubbing column. . Thus, the overhead gas containing hydrogen and nitrogen has low levels of CH4 and CO (at the ppm level) corresponding to the need of the ammonia production unit. In column vat, the liquid containing impurities CH4 and CO and a portion of N2 coming from washing is expanded at low pressure and used to condense nitrogen to serve as washing liquid. The idea put forward in this proposal for an invention would make it possible to separate the CH4 from the synthesis gas upstream of the washing step and thus to increase the CH4 content of the separated CH4 fluid and / or to increase the yield. It is planned to recover CH4 by recycling it in a synthesis gas production system to increase the production of H2 molecule, for example by using it as a feed gas for a reforming furnace. , an autothermal reactor or a partial oxidation reactor. The higher the concentration of CH4, the greater the efficiency of the overall system. In fact, by lowering the content, in particular N2, in the CH4-rich fluid, the investment of the synthesis gas generation unit is reduced from the CH4-rich fluid and less energy is consumed to preheat the fluid. rich in CH4. Likewise, the higher the recovery efficiency of CH4, the greater the amount of hydrogen produced. This improves the overall efficiency of the syngas production system. Thus, when the synthesis gas is produced mainly by a coal gasification reactor, the invention proposal makes it possible to increase the purity and / or the recovery rate of the residual CH4 contained in the synthesis gas in order to increase the production of gas. total synthesis or to reduce the investment of the gasification unit. The process is aimed at increasing the concentration of methane and / or the recovery yield of CH4 in the gas produced by partial condensation, in order to reduce the CH4 content in the fluid to be sent to the washing column.
Selon un objet de l'invention, il est prévu un procédé de séparation cryogénique par lavage à l'azote pour la production d'un mélange d'hydrogène et d'azote contenant moins que 1% de CH4 et/ou moins que 1% de CO dans lequel : i) on refroidit un gaz de synthèse contenant de l'hydrogène, de l'azote, du méthane et moins que 5% de monoxyde de carbone dans un échangeur de chaleur et on le condense partiellement pour produire un gaz enrichi en hydrogène et un premier liquide enrichi en méthane ii) on condense partiellement le gaz enrichi en hydrogène pour produire 10 une vapeur enrichie en hydrogène et un deuxième liquide enrichi en méthane iii) on envoie au moins une partie de la vapeur enrichie en hydrogène vers une colonne de lavage iv) on envoie de l'azote liquide en tête de la colonne de lavage y) on soutire le mélange d'hydrogène et d'azote en tête de la colonne 15 de lavage vi) on mélange le premier et le deuxième liquides enrichis en méthane, on détend le mélange et on en réchauffe au moins une partie dans l'échangeur de chaleur pour former un gaz riche en méthane. 20 Selon d'autres objets facultatifs : - le premier liquide enrichi en méthane et/ou le deuxième liquide enrichi en méthane contiennent au moins 70% de méthane. - on détend un liquide de cuve de la colonne et on le vaporise ou on vaporise un liquide dérivé du liquide dans l'échangeur de chaleur. 25 Selon un autre objet de l'invention, il est prévu un appareil de séparation cryogénique par lavage à l'azote pour la production d'un mélange d'hydrogène et d'azote contenant moins que 1% de CH4 et/ou moins que 1% de CO comprenant un échangeur de chaleur, des moyens pour envoyer un gaz de synthèse contenant de l'hydrogène, de l'azote, du méthane et moins que 5% de 30 monoxyde de carbone se refroidir et se condenser partiellement, un premier pot séparateur, des moyens pour envoyer le fluide partiellement condensé dans l'échangeur au premier pot pour produire un gaz enrichi en hydrogène et un premier liquide enrichi en méthane, des moyens pour condenser partiellement le gaz enrichi en hydrogène pour produire une vapeur enrichie en hydrogène et un deuxième liquide enrichi en méthane, un deuxième pot séparateur pour séparer la vapeur et le deuxième liquide, une colonne de lavage, des moyens pour envoyer au moins une partie de la vapeur enrichie en hydrogène du deuxième pot séparateur vers la colonne de lavage, des moyens pour envoyer de l'azote liquide en tête de la colonne de lavage, des moyens pour soutirer le mélange d'hydrogène et d'azote en tête de la colonne de lavage, des moyens pour mélanger le premier et le deuxième liquides enrichis en méthane, des moyens pour détendre le mélange ou les liquides à mélanger et des moyens pour envoyer au moins une partie du mélange détendu ou des liquides 10 détendus dans l'échangeur de chaleur pour former un gaz riche en méthane. L'appareil peut comprendre des moyens de détente d'un liquide de cuve de la colonne reliés à l'échangeur de chaleur, pour permettre la vaporisation du liquide. L'invention sera décrite de manière plus détaillée en se référant à la 15 figure, qui montre un procédé selon l'invention. Un gaz de synthèse 1 est produit par une unité de lavage de type Rectisol R et épuré dans une unité d'épuration E. L'unité E est régénérée par un débit d'azote. Le gaz de synthèse est épuré en CO2 et méthanol pour former un gaz 3. Il contient moins que 5% de monoxyde de carbone ainsi que de 20 l'azote, de l'hydrogène et du méthane. Le gaz de synthèse à un contenant forte en CH4 (entre 1`)/0 et 25%) est refroidi dans un échangeur de chaleur E2 à un niveau de température cryogénique supérieur à -182°C. La phase liquide est un premier liquide 7 enrichi en méthane qui contient majoritairement de CH4 (environ 80%) qui est séparé du gaz de synthèse dans un premier pot 25 séparateur P1. Pour augmenter le taux de la récupération de CH4, la phase vapeur 9 provenant du premier pot séparateur est refroidie à nouveau à environ -182°C dans l'échangeur de chaleur E1. La phase liquide est un deuxième liquide 13 enrichi en méthane qui contient majoritairement de CH4 (environ 70%). Elle est séparé dans un deuxième pot séparateur P2. 30 Les deux liquides 7, 13 avec forte teneur de CH4 seront détendus dans les vannes V1, V2, envoyés à un troisième pot séparateur P3 et recyclés aux systèmes de production de gaz de synthèse La phase vapeur 11 du deuxième pot séparateur P2 est traitée dans une colonne de lavage au N2 C où on injecte du N2 liquide en tête de colonne par une vanne V5, ce qui permet d'abaisser la teneur en CH4 et CO dans la vapeur 21 produite en tête de colonne de lavage d'un mélange hydrogène et azote avec de très faibles teneurs en CH4 et en CO, correspondant au besoin de l'unité de production d'ammoniac (donc avec un rapport H2/N2 d'environ 3).According to one object of the invention, there is provided a method of cryogenic separation by washing with nitrogen for the production of a mixture of hydrogen and nitrogen containing less than 1% of CH4 and / or less than 1% CO in which: i) a synthesis gas containing hydrogen, nitrogen, methane and less than 5% carbon monoxide is cooled in a heat exchanger and partially condensed to produce an enriched gas in hydrogen and a first methane-enriched liquid ii) partially condensing the hydrogen-enriched gas to produce a hydrogen-enriched vapor and a second methane-enriched liquid iii) sending at least a portion of the hydrogen-enriched vapor to a hydrogen-enriched vapor washing column iv) liquid nitrogen is sent to the top of the washing column y) the mixture of hydrogen and nitrogen is withdrawn at the top of the washing column vi) the first and second liquids are mixed together enriched with methane, relaxes the m and warming at least a portion of the heat exchanger to form a methane-rich gas. According to other optional objects: the first liquid enriched in methane and / or the second liquid enriched in methane contain at least 70% methane. - A tank liquid is expanded from the column and vaporized or vaporized liquid derived from the liquid in the heat exchanger. According to another object of the invention, there is provided a nitrogen washing cryogenic separation apparatus for the production of a mixture of hydrogen and nitrogen containing less than 1% CH4 and / or less than 1% CO comprising a heat exchanger, means for sending a synthesis gas containing hydrogen, nitrogen, methane and less than 5% carbon monoxide to cool and partially condense, a first separator pot, means for supplying the partially condensed fluid in the exchanger to the first pot to produce a hydrogen-enriched gas and a first methane-enriched liquid, means for partially condensing the hydrogen-enriched gas to produce a hydrogen-enriched vapor and a second methane-enriched liquid, a second separator pot for separating the vapor and the second liquid, a washing column, means for sending at least a portion of the hydrogen-enriched vapor of the two x separator pot to the washing column, means for sending liquid nitrogen at the top of the washing column, means for withdrawing the hydrogen and nitrogen mixture at the top of the washing column, means for mixing the first and second methane enriched liquids, means for expanding the mixture or liquids to be mixed, and means for sending at least a portion of the expanded mixture or slack liquids into the heat exchanger to form a rich gas in methane. The apparatus may include means for expanding a column bottom liquid connected to the heat exchanger to allow vaporization of the liquid. The invention will be described in more detail with reference to the figure, which shows a method according to the invention. A synthesis gas 1 is produced by a washing unit of Rectisol R type and purified in a purification unit E. The unit E is regenerated by a nitrogen flow. The synthesis gas is purified to CO2 and methanol to form a gas 3. It contains less than 5% carbon monoxide as well as nitrogen, hydrogen and methane. Synthesis gas with a strong CH4 (between 1%) and 0% (25%) container is cooled in a heat exchanger E2 at a cryogenic temperature above -182 ° C. The liquid phase is a first methane-enriched liquid 7 which contains predominantly CH.sub.4 (about 80%) which is separated from the synthesis gas in a first separator pot P1. To increase the rate of CH4 recovery, the vapor phase 9 from the first separator pot is cooled back to about -182 ° C in the heat exchanger E1. The liquid phase is a second liquid 13 enriched in methane which contains predominantly CH4 (about 70%). It is separated in a second separator pot P2. The two liquids 7, 13 with a high content of CH4 will be expanded in the valves V1, V2, sent to a third separator pot P3 and recycled to the synthesis gas production systems. The vapor phase 11 of the second separator pot P2 is treated in a N 2 C washing column where liquid N 2 is injected at the top of the column via a valve V 5, which makes it possible to lower the content of CH 4 and CO in the steam 21 produced at the top of the column for washing a hydrogen mixture and nitrogen with very low levels of CH4 and CO, corresponding to the need for the ammonia production unit (thus with an H2 / N2 ratio of about 3).
En cuve de colonne de lavage, le liquide contenant majoritairement de N2 et les impuretés est détendu à faible pression dans une vanne V3, envoyé à un pot séparateur P4 et alimenté également en azote liquide LIN. Le liquide 31 du pot séparateur P4 se réchauffe dans l'échangeur de chaleur E2,puis est mélangé avec le gaz 21 du pot séparateur P4 et réchauffé à température ambiant pour former un fluide 33 qui se chauffe dans l'échangeur El pour être utilisé dans le réseau de combustible. Le liquide 17 et le gaz 19 du troisième pot séparateur P3 sont réchauffés dans l'échangeur E2, mélangés et chauffés dans l'échangeur El pour former le débit 35.In the washing column tank, the liquid containing predominantly N 2 and the impurities is expanded at low pressure in a valve V3, sent to a separator pot P4 and also supplied with liquid nitrogen LIN. The liquid 31 of the separator pot P4 heats up in the heat exchanger E2, then is mixed with the gas 21 of the separator pot P4 and heated to ambient temperature to form a fluid 33 which is heated in the exchanger E1 for use in the fuel network. The liquid 17 and the gas 19 of the third separator pot P3 are heated in the exchanger E2, mixed and heated in the exchanger El to form the flow 35.
De l'azote gazeux HP N2 se condense dans l'échangeur El pour former le débit 15 qui se refroidit dans l'échangeur E2. Il est divisé en deux, une partie allant en tête de colonne par la canne V5 et le reste 19 allant par la V4 pour être mélangé avec le gaz de tête 21 pour ajuster les teneurs en tête. Le mélange forme 23 se réchauffe dans l'échangeur E2 puis est divisé en deux.Nitrogen gas HP N2 condenses in the exchanger E1 to form the flow 15 which cools in the exchanger E2. It is divided in two, a portion going to the top of the column by the rod V5 and the remainder 19 going through the V4 to be mixed with the overhead gas 21 to adjust the contents at the head. The mixture forms 23 is heated in the exchanger E2 and is divided into two.
Une partie 25 se réchauffe dans l'unité R et le reste 27 se réchauffe dans l'échangeur E1, est détendu dans une vanne V6 et est mélangé de nouveau avec le débit 25 pour former le gaz 29 de synthèse d'ammoniac.Part 25 warms up in the unit R and the remainder 27 warms up in the exchanger E1, is expanded in a valve V6 and is mixed again with the flow 25 to form the ammonia synthesis gas 29.
Claims (5)
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| Application Number | Priority Date | Filing Date | Title |
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| FR1361069A FR3013106A1 (en) | 2013-11-13 | 2013-11-13 | CRYOGENIC SEPARATION PROCESS FOR THE PRODUCTION OF A MIXTURE OF HYDROGEN AND NITROGEN CONTAINING LOW CO AND CH4 CONTENT |
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| FR1361069A FR3013106A1 (en) | 2013-11-13 | 2013-11-13 | CRYOGENIC SEPARATION PROCESS FOR THE PRODUCTION OF A MIXTURE OF HYDROGEN AND NITROGEN CONTAINING LOW CO AND CH4 CONTENT |
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| FR3054304A1 (en) * | 2016-07-25 | 2018-01-26 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | METHOD AND APPARATUS FOR CLEANING AT CRYOGENIC TEMPERATURE FOR THE PRODUCTION OF A MIXTURE OF HYDROGEN AND NITROGEN |
| FR3089429A1 (en) * | 2018-12-11 | 2020-06-12 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Method and apparatus for purifying a hydrogen-rich gas |
| CN111536758A (en) * | 2020-04-29 | 2020-08-14 | 中科瑞奥能源科技股份有限公司 | Coupling system and method for liquid nitrogen washing and cryogenic separation |
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| US2936593A (en) * | 1956-04-27 | 1960-05-17 | Air Liquide | Process for the production of ammonia synthesis gas |
| WO2012097497A1 (en) * | 2011-01-17 | 2012-07-26 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Process and apparatus for production of ammonia synthesis gas and pure methane by cryogenic separation |
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| US2936593A (en) * | 1956-04-27 | 1960-05-17 | Air Liquide | Process for the production of ammonia synthesis gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| FR3054304A1 (en) * | 2016-07-25 | 2018-01-26 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | METHOD AND APPARATUS FOR CLEANING AT CRYOGENIC TEMPERATURE FOR THE PRODUCTION OF A MIXTURE OF HYDROGEN AND NITROGEN |
| WO2018020091A1 (en) * | 2016-07-25 | 2018-02-01 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Method and apparatus for scrubbing at cryogenic temperature in order to produce a mixture of hydrogen and nitrogen |
| FR3089429A1 (en) * | 2018-12-11 | 2020-06-12 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Method and apparatus for purifying a hydrogen-rich gas |
| CN111536758A (en) * | 2020-04-29 | 2020-08-14 | 中科瑞奥能源科技股份有限公司 | Coupling system and method for liquid nitrogen washing and cryogenic separation |
| CN111536758B (en) * | 2020-04-29 | 2024-01-30 | 中科瑞奥能源科技股份有限公司 | Coupling system and method for liquid nitrogen washing and cryogenic separation |
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