[go: up one dir, main page]

EP2864240A1 - Method and installation for the combined production of ammonia synthesis gas and carbon dioxide - Google Patents

Method and installation for the combined production of ammonia synthesis gas and carbon dioxide

Info

Publication number
EP2864240A1
EP2864240A1 EP13733351.4A EP13733351A EP2864240A1 EP 2864240 A1 EP2864240 A1 EP 2864240A1 EP 13733351 A EP13733351 A EP 13733351A EP 2864240 A1 EP2864240 A1 EP 2864240A1
Authority
EP
European Patent Office
Prior art keywords
gas
carbon dioxide
unit
ammonia
methane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13733351.4A
Other languages
German (de)
French (fr)
Inventor
Arthur Darde
Richard Dubettier-Grenier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Publication of EP2864240A1 publication Critical patent/EP2864240A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/025—Preparation or purification of gas mixtures for ammonia synthesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/245—Stationary reactors without moving elements inside placed in series
    • 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
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/50—Carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis in the gas phase
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis in the gas phase
    • C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis in the gas phase
    • C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
    • C01C1/0488—Processes integrated with preparations of other compounds, e.g. methanol, urea or with processes for power generation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
    • C07C273/10—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds combined with the synthesis of ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24—Stationary reactors without moving elements inside
    • 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
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • 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
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/042—Purification by adsorption on solids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/042—Purification by adsorption on solids
    • C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • 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
    • C01B2203/0475—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
    • C01B2203/048—Composition of the impurity the impurity being an organic 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
    • C01B2203/04—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
    • C01B2203/0495—Composition of the impurity the impurity being water
    • 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
    • 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
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0872—Methods of cooling
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • 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
    • 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
    • C01B2203/148—Details of the flowsheet involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0001—Separation or purification processing
    • C01B2210/0009—Physical processing
    • C01B2210/0014—Physical processing by adsorption in solids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a method and installation for the combined production of synthesis gas of ammonia and carbon dioxide from a hydrocarbon source. More particularly, the present invention relates to a process for the combined production of synthesis gas of ammonia and carbon dioxide from a synthesis gas obtained by reforming hydrocarbons, and in particular natural gas.
  • the invention also relates to a method and an integrated production plant for ammonia and carbon dioxide and a method and a plant for producing urea.
  • step 4 When it is desired to recover the CO2 extracted in step 4 (for example to facilitate the extraction of oil or for a chemical production such as urea, etc.) or if it is desired to sequester it to reduce emissions of greenhouse gases, it is necessary to add a step of compression and drying of the CO2 extracted in step 4.
  • the proposed invention aims to significantly reduce the cost of production of NH 3 when the CO2 must be compressed to be valued as mentioned above.
  • a process for the combined production of synthesis gas of ammonia and carbon dioxide from a mixture of hydrocarbons comprising at least:
  • PSA waste containing carbon dioxide, nitrogen, methane and carbon monoxide, at a pressure of the order of 1 to 3 bar abs
  • a step of treating said PSA waste to obtain a fluid enriched in carbon dioxide comprising at least:
  • each of the steps includes itself: a condensation step of all or part of the CO2 contained in the gas from the previous step, followed by
  • step or steps are carried out at temperatures between room temperature and -56 ° C,
  • the depleted flow rate of CO2 is sent to methanation at a pressure of at least 35 bar.
  • CO2 is sent to the adsorption unit by pressure modulation.
  • the process comprises a reverse conversion step to the synthesis gas vapor to oxidize most of the carbon monoxide it contains to carbon dioxide, with corresponding production of hydrogen
  • the process comprises a step of reforming the hydrocarbon mixture to obtain synthesis gas containing at least carbon dioxide, hydrogen, carbon monoxide, methane, and water vapor;
  • the gas containing methane and nitrogen is returned to the reforming step.
  • all the nitrogen sent to the treatment unit is contained in the at least a portion of the hydrogen enriched stream and the at least a portion of the nitrogen and methane containing gas mixed to form a synthesis gas; 'ammonia.
  • Ammonia is reacted with carbon dioxide to produce urea.
  • an apparatus for the combined production of synthesis gas of ammonia and carbon dioxide from a mixture of hydrocarbons comprising at least:
  • PSA waste a waste gas containing carbon dioxide, nitrogen, methane and carbon monoxide
  • a processing unit of said PSA waste to obtain a fluid enriched in carbon dioxide comprising at least:
  • a PSA waste drying unit compressed by removing the water contained to obtain a dry gas
  • step or steps are carried out at temperatures between room temperature and -56 ° C,
  • a CO2 depletion unit of a gaseous phase resulting from at least one separation step, for example by permeation, to produce a depleted flow rate of CO2 and a flow enriched with CO2
  • the apparatus may include means for sending the CO2 enriched flow from the CO2 depletion step to the pressure modulation adsorption unit.
  • an apparatus for producing ammonia and carbon dioxide as described above comprising a processing unit for treating ammonia synthesis gas to produce a flow rate of ammonia and a gas containing methane and nitrogen.
  • the apparatus may include means for returning the gas containing methane and nitrogen to the reforming step.
  • the apparatus may include a synthesis gas reverse conversion unit for oxidizing most of the carbon monoxide it contains to carbon dioxide, with corresponding hydrogen production.
  • the apparatus may comprise a reforming unit of the hydrocarbon mixture for obtaining synthesis gas containing at least carbon dioxide, hydrogen, carbon monoxide, methane and water vapor.
  • the apparatus may include a unit in which the ammonia is reacted with the carbon dioxide to produce urea.
  • the solution according to the invention consists in using the incondensable gases of a process for producing carbon dioxide by separation at low temperature to supply an ammonia synthesis production unit.
  • the PSA residue contains a quantity of CO2 of about 45% from reforming and reverse conversion (the exact content of CO2 is naturally a function of the composition of the mixture initial hydrocarbons).
  • the process then makes it possible, starting from the residual gas of the PSA, whose pressure is typically less than 2 bar, to dispose, thanks to the compression of a gas, at a total pressure of between 40 and 80 bar, corresponding to a partial pressure of CO2. between 15 and 40 bar, compatible with cryogenic purification. These pressures will make it possible to use the fluids in the rest of the process without having to resort to additional compressions.
  • the PSA waste is purified by partial condensation and optionally by permeation to produce a liquid flow rich in CO2.
  • This liquid can, thanks to appropriate complementary treatments, be used or sequestered on site or nearby in gaseous form; it can be exported for use or sequestered in gaseous or liquid form. It can particularly and particularly advantageously be used in the food industry, through a suitable purification.
  • all or part of the liquid is vaporized after expansion, with recovery of cold, to produce CO2 in gaseous form under pressure between 10 and 35 bar.
  • the recovered cold is advantageously used for the cooling of process fluids in addition to the refrigerating apparatus.
  • the CO2 can then be compressed to be transported by pipeline to a site of use and / or sequestration.
  • the process is particularly advantageous when it is used to optimize the production of ammonia synthesis gas and jointly produce carbon dioxide.
  • FIG. 1 represents a functional diagram illustrating an embodiment of the invention for the production of synthesis gas of ammonia and, respectively, of carbon dioxide, for example carbon dioxide to be sequestered.
  • the feedstock to the process consists of a mixture of hydrocarbons - here natural gas (NG) - the hydrocarbon stream 1 feeds a plant 3 comprising a desulfurization unit, a pre-reformer to produce a pre-reformed mixture, mixture consisting essentially of methane, hydrogen, carbon monoxide, carbon dioxide and water, a reforming module fed by the pre-reformed mixture which produces a synthesis gas substantially containing hydrogen, monoxide of carbon, carbon dioxide, methane and water vapor and a reverse conversion module.
  • NG natural gas
  • the synthesis gas is cooled and then the cooled gas is treated in this inverse conversion module, where the CO is converted to H 2 and CO2.
  • the gaseous mixture 5 leaving the plant 3 is cooled and then treated in a hydrogen purification unit 7 of pressure swing adsorption or PSA type, to obtain a gaseous stream enriched with hydrogen 9 at a purity at least equal to 98% and a residue gas 1 1 - waste PSA- containing carbon dioxide, methane, nitrogen, argon, hydrogen and carbon monoxide.
  • This residual PSA 1 1 is available at a pressure of the order of 1 to 3 bar abs, it contains substantially all the CO2 co-produced during the reforming and reverse conversion steps.
  • the average composition of the PSA 1 1 waste is close to: CO 2 : 45% - CO: 12% - H2: 23% - CH 4 : 17% - H 2 O: 1% - N 2 : 2%.
  • CO2 content is between 42 and 48%, the content of H 2 varies between 20 and 26%, the contents of other constituents remaining approximately constant.
  • the PSA residue 1 1 is then purified in a purification unit 13.
  • the PSA 11 1 waste is first compressed in a compression module of the purification unit, to obtain a residual PSA compressed . It is compressed to about 60 bar, which ensures a partial pressure of CO2 of the order of 27 bar. Then it is freed from its heavy impurities in an adsorption module of the purification unit, by a succession of regenerable adsorptions for example, one thus obtains a purified compressed waste which is then dried in a drying module of the purification unit for obtaining a compressed waste, freed from heavy impurities and dried.
  • This waste is then cooled to be separated by liquefaction in a separation module forming part of the purification unit, which makes it possible to obtain a liquid containing essentially liquid CO2 and a gaseous mixture containing an uncondensed fraction of CO2. than lighter compounds called incondensable.
  • the cooling of the waste 1 1 is carried out by countercurrent circulation of the cold fluids resulting from the cryogenic purification and / or by heat exchange with an associated external refrigerating unit.
  • the liquid contains essentially CO2, however, in order to obtain pure CO2, the liquid results from a distillation in order to rid it of the light impurities entrained in the liquid phase. For this, the waste can be expanded to 23 bar before feeding the distillation column.
  • the gas phase 17 obtained at the end of the separation contains the light impurities of the charge 1 and is at least 40 bar abs; warmed to room temperature in the heat exchangers, it is the purge of incondensables, available at a pressure of 58 bar.
  • the composition of the purge is of the order of: CO 2 : 21% - CO: 18% - H 2: 36% - CH 4 : 24% - N 2 : 1%.
  • the purge of incondensables 17 is then treated in the adsorption or permeation module of a CO2 depletion unit 19 for reduce its carbon dioxide content.
  • a product gas 21 has a reduced content of carbon dioxide.
  • the other product gas 20, enriched in CO2 and rich in hydrogen, is sent to the unit PSA 7 to improve its performance, without being mixed upstream with the flow 5.
  • the efficiency of the PSA unit 7 is very low because of the strong hold in N 2, one way of improving it is to introduce the gas (possibly being a permeate), which is certainly richer in H2 that the PSA feed, at the right time of the cycle, to improve the performance of PSA.
  • the PSA unit differs from the usual H 2 PSA that must stop CO / CO 2 and N 2 .
  • the unit 7 stops the CO and the CO2, but can let the nitrogen pass, which makes it possible not to have to penalize itself on the yield H 2 of the unit PSA 7.
  • the gas 21 is then treated by methanation in a methanation unit 23 to convert the carbon dioxide and carbon monoxide residues into methane, forming a gas.
  • the gas is mixed with the pure hydrogen 9 to form an ammonia synthesis gas 27.
  • the ammonia synthesis gas 27 is sent to an ammonia synthesis unit 29 to produce ammonia 31.
  • the ammonia synthesis unit also produces a gas 33 containing methane, nitrogen, argon, and hydrogen which is returned to unit 3.
  • ammonia 31 and carbon dioxide 15 can feed a urea production unit 35.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Separation Of Gases By Adsorption (AREA)

Abstract

In a method for the combined production of ammonia synthesis gas and carbon dioxide from a mixture of hydrocarbons, the cooled mixture from a reverse conversion is separated in an adsorption unit by pressure modulation (or PSA) producing a hydrogen-enriched flow (9) having a purity at least equal to 98% and a residual gas (11), the residual gas is processed to produce carbon dioxide and a gas containing nitrogen and methane (25) and at least a portion of the hydrogen-enriched flow and at least a portion of the gas containing nitrogen and methane are mixed to form an ammonia synthesis gas (27).

Description

Procédé et installation pour la production combinée de gaz de synthÚse d'ammoniac et de dioxyde de carbone  Process and installation for the combined production of syngas of ammonia and carbon dioxide
La présente invention concerne un procédé et installation de production combinée de gaz de synthÚse d'ammoniac et de dioxyde de carbone à partir d'une source d'hydrocarbures. Plus particuliÚrement, la présente invention concerne un procédé de production combinée de gaz de synthÚse d'ammoniac et de dioxyde de carbone à partir d'un gaz de synthÚse obtenu par reformage d'hydrocarbures, et notamment de gaz naturel. The present invention relates to a method and installation for the combined production of synthesis gas of ammonia and carbon dioxide from a hydrocarbon source. More particularly, the present invention relates to a process for the combined production of synthesis gas of ammonia and carbon dioxide from a synthesis gas obtained by reforming hydrocarbons, and in particular natural gas.
L'invention concerne également un procédé et une installation de production intégrée d'ammoniac et de dioxyde de carbone et un procédé et une installation de production d'urée.  The invention also relates to a method and an integrated production plant for ammonia and carbon dioxide and a method and a plant for producing urea.
Tous les pourcentages concernant des puretés sont des pourcentages molaires.  All percentages for purities are molar percentages.
Il est connu de WO-A-06/054008 de produire du dioxyde de carbone à partir d'un résiduaire de PSA traitant un gaz issu d'une conversion inverse.  It is known from WO-A-06/054008 to produce carbon dioxide from a PSA waste treating a gas resulting from an inverse conversion.
Les principales étapes de la synthÚse d'ammoniac sont :  The main stages of ammonia synthesis are:
1 . reformage à la vapeur de gaz naturel (ou autre combustible carboné).  1. steam reforming of natural gas (or other carbonaceous fuel).
2. second reformage/ oxydation partielle à l'air, afin d'introduire de l'azote pour la réaction de synthÚse d'ammoniac.  2. second reforming / partial oxidation in air, in order to introduce nitrogen for the ammonia synthesis reaction.
3. shift du CO en CO2 et H2 sur un catalyseur. 3. shift of CO to CO 2 and H 2 on a catalyst.
4. extraction du CO2 par lavage à l'aide d'un solvant (aMDEA Ÿ, procédé Benfield, etc.) 4. extraction of CO 2 by washing with a solvent (aMDEA Ÿ, Benfield process, etc.)
5. méthanation des traces de CO et CO2 en CH et H2O sur un catalyseur grùce au fort excÚs d'hydrogÚne (CO et CO2 étant des poisons pour le catalyseur). 5. methanation of traces of CO and CO 2 in CH and H 2 O on a catalyst thanks to the large excess of hydrogen (CO and CO 2 being poisons for the catalyst).
6. synthÚse de l'ammoniac avec deux variantes possibles :  6. Ammonia synthesis with two possible variants:
a. séchage + lavage à l'azote pour ajuster le ratio H2/N2 à 3 et extraction du CH , Argon et N2 excédentaire + boucle de synthÚse de l'NH3 via des réacteurs catalytiques, b. ou bien : boucle de synthÚse de l'NH3 via des réacteurs catalytiques + traitement de la purge évacuant CH , Argon et excÚs d'N2 sur un PSA pour en récupérer l'H2. at. drying + washing with nitrogen to adjust the H 2 / N 2 to 3 ratio and extraction of the excess CH, Argon and N 2 + synthesis loop of NH 3 via catalytic reactors, b. or else: synthesis loop of NH 3 via catalytic reactors + treatment of the purging purge CH, Argon and excess of N 2 on a PSA to recover the H 2 .
Lorsque l'on souhaite valoriser le CO2 extrait dans l'étape 4 (par exemple pour faciliter l'extraction de pétrole ou pour une production chimique comme de l'urée, etc.) ou si l'on souhaite le séquestrer pour réduire les émissions de gaz à effet de serre, il faut ajouter une étape de compression et séchage du CO2 extrait à l'étape 4.  When it is desired to recover the CO2 extracted in step 4 (for example to facilitate the extraction of oil or for a chemical production such as urea, etc.) or if it is desired to sequester it to reduce emissions of greenhouse gases, it is necessary to add a step of compression and drying of the CO2 extracted in step 4.
L'invention proposĂ©e vise Ă  rĂ©duire significativement le coĂ»t de production de l'NH3 lorsque le CO2 doit ĂȘtre comprimĂ© pour ĂȘtre valorisĂ© comme mentionnĂ© plus haut. The proposed invention aims to significantly reduce the cost of production of NH 3 when the CO2 must be compressed to be valued as mentioned above.
Il existe donc un besoin pour un procédé économiquement viable de production de gaz de synthÚse d'ammoniac et de production de dioxyde de carbone.  There is therefore a need for an economically viable process for producing ammonia synthesis gas and producing carbon dioxide.
Selon un objet de l'invention, il est prévu un procédé pour la production combinée de gaz de synthÚse d'ammoniac et de dioxyde de carbone à partir d'un mélange d'hydrocarbures, comportant au moins :  According to one object of the invention, there is provided a process for the combined production of synthesis gas of ammonia and carbon dioxide from a mixture of hydrocarbons, comprising at least:
une étape de purification du mélange refroidi issu de la/d'une conversion inverse dans une unité d'adsorption par modulation de pression (ou PSA) permettant l'obtention d'un flux enrichi en hydrogÚne à une pureté au moins égale à 98% et d'un gaz résiduaire dit « résiduaire du PSA » contenant du dioxyde de carbone, de l'azote, du méthane et du monoxyde de carbone, à une pression de l'ordre de 1 à 3 bar abs,  a step of purifying the cooled mixture resulting from the / an inverse conversion in a pressure modulation adsorption unit (or PSA) allowing a hydrogen enriched stream to be obtained with a purity of at least 98%; and a waste gas called "PSA waste" containing carbon dioxide, nitrogen, methane and carbon monoxide, at a pressure of the order of 1 to 3 bar abs,
ainsi qu'une étape de traitement dudit résiduaire du PSA pour l'obtention d'un fluide enrichi en dioxyde de carbone, comportant au moins :  and a step of treating said PSA waste to obtain a fluid enriched in carbon dioxide, comprising at least:
une étape de compression du résiduaire du PSA jusqu'à une pression supérieure à la pression du reformage et telle que la pression partielle du CO2 contenu soit comprise entre 25 et 35 bar environ ;  a step of compressing the PSA waste to a pressure greater than the reforming pressure and such that the partial pressure of the CO2 content is between about 25 and 35 bar;
une étape de séchage du résiduaire du PSA comprimé par élimination de l'eau contenue pour l'obtention d'un gaz sec ;  a step of drying the compressed PSA waste by removing the water contained to obtain a dry gas;
une étape ou plusieurs étapes successives de condensation/séparation, telle(s) que  a step or several successive stages of condensation / separation, such that
‱ chacune des Ă©tapes comprend elle-mĂȘme : une Ă©tape de condensation de tout ou partie du CO2 contenu dans le gaz provenant de l'Ă©tape prĂ©cĂ©dente, suivie par ‱ each of the steps includes itself: a condensation step of all or part of the CO2 contained in the gas from the previous step, followed by
une étape de séparation du condensùt riche en CO2 issu de la séparation d'avec la phase gazeuse contenant les composés incondensables, éventuellement par distillation  a step of separation of the CO2-rich condensate resulting from the separation from the gas phase containing the incondensable compounds, optionally by distillation
‱ et,  ‱ and,
la ou les Ă©tapes sont mises en Ɠuvre Ă  des tempĂ©ratures comprises entre la tempĂ©rature ambiante et -56°C,  the step or steps are carried out at temperatures between room temperature and -56 ° C,
une étape d'appauvrissement en CO2 d'une phase gazeuse issue d'au moins une étape de séparation, par exemple par perméation, pour produire un débit appauvri en CO2 et un débit enrichi en CO2  a stage of CO2 depletion of a gas phase resulting from at least one separation stage, for example by permeation, to produce a depleted flow rate of CO2 and a flow enriched in CO2
une étape de méthanation du débit appauvri en CO2 pour produire un gaz contenant de l'azote et du méthane et  a step of methanation of the depleted CO2 flow to produce a gas containing nitrogen and methane and
une étape de mélanger au moins une partie du flux enrichi en hydrogÚne et au moins une partie du gaz contenant de l'azote et du méthane pour former un gaz de synthÚse d'ammoniac.  a step of mixing at least a portion of the hydrogen enriched stream and at least a portion of the nitrogen and methane containing gas to form an ammonia synthesis gas.
Selon d'autres aspects facultatifs :  According to other optional aspects:
le débit appauvri en CO2 est envoyé à la méthanation à une pression d'au moins 35 bars.  the depleted flow rate of CO2 is sent to methanation at a pressure of at least 35 bar.
- le débit enrichi en CO2 provenant de l'étape d'appauvrissement en the CO2 enriched flow from the depletion stage in
CO2 est envoyé à l'unité d'adsorption par modulation de pression. CO2 is sent to the adsorption unit by pressure modulation.
le procédé comprend une étape de conversion inverse à la vapeur de gaz de synthÚse pour oxyder la majeure partie du monoxyde de carbone qu'il contient en dioxyde de carbone, avec production correspondante d'hydrogÚne  the process comprises a reverse conversion step to the synthesis gas vapor to oxidize most of the carbon monoxide it contains to carbon dioxide, with corresponding production of hydrogen
le procédé comprend une étape de reformage du mélange d'hydrocarbures pour l'obtention de gaz de synthÚse contenant au moins du dioxyde de carbone, de l'hydrogÚne, du monoxyde de carbone, du méthane, et de la vapeur d'eau ;  the process comprises a step of reforming the hydrocarbon mixture to obtain synthesis gas containing at least carbon dioxide, hydrogen, carbon monoxide, methane, and water vapor;
Selon un autre objet de l'invention, il est prévu un procédé de production d'ammoniac et de dioxyde de carbone tel que décrit ci-dessus dans lequel on traite le gaz de synthÚse d'ammoniac dans une unité de traitement pour produire un débit d'ammoniac et un gaz contenant du méthane et de l'azote. Eventuellement : According to another object of the invention, there is provided a method for producing ammonia and carbon dioxide as described above in which ammonia synthesis gas is treated in a treatment unit to produce a flow rate. ammonia and a gas containing methane and nitrogen. Eventually :
on renvoie le gaz contenant du méthane et de l'azote vers l'étape de reformage.  the gas containing methane and nitrogen is returned to the reforming step.
tout l'azote envoyé à l'unité de traitement est contenu dans l'au moins une partie du flux enrichi en hydrogÚne et l'au moins une partie du gaz contenant de l'azote et du méthane mélangés pour former un gaz de synthÚse d'ammoniac.  all the nitrogen sent to the treatment unit is contained in the at least a portion of the hydrogen enriched stream and the at least a portion of the nitrogen and methane containing gas mixed to form a synthesis gas; 'ammonia.
on fait réagir l'ammoniac avec le dioxyde de carbone pour produire de l'urée.  Ammonia is reacted with carbon dioxide to produce urea.
Selon un autre objet de l'invention, il est prévu un appareil pour la production combinée de gaz de synthÚse d'ammoniac et de dioxyde de carbone à partir d'un mélange d'hydrocarbures, comportant au moins :  According to another object of the invention, there is provided an apparatus for the combined production of synthesis gas of ammonia and carbon dioxide from a mixture of hydrocarbons, comprising at least:
une unité de purification du mélange refroidi issu d'une conversion inverse dans une unité d'adsorption par modulation de pression (ou PSA) permettant l'obtention d'un flux enrichi en hydrogÚne à une pureté au moins égale à 98% et d'un gaz résiduaire dit « résiduaire du PSA » contenant du dioxyde de carbone, de l'azote, du méthane et du monoxyde de carbone, à une pression de l'ordre de 1 à 3 bar abs,  a unit for purifying the cooled mixture resulting from an inverse conversion in a pressure modulation adsorption unit (or PSA) allowing a hydrogen enriched stream to be obtained with a purity of at least 98% and of a waste gas called "PSA waste" containing carbon dioxide, nitrogen, methane and carbon monoxide, at a pressure of the order of 1 to 3 bar abs,
ainsi qu'une unité de traitement dudit résiduaire du PSA pour l'obtention d'un fluide enrichi en dioxyde de carbone, comportant au moins :  and a processing unit of said PSA waste to obtain a fluid enriched in carbon dioxide, comprising at least:
une unité de compression du résiduaire du PSA jusqu'à une pression supérieure à la pression du reformage et telle que la pression partielle du CO2 contenu soit comprise entre 25 et 35 bar environ ;  a unit for compressing the PSA waste to a pressure greater than the reforming pressure and such that the partial pressure of the CO2 content is between approximately 25 and 35 bar;
une unité de séchage du résiduaire du PSA comprimé par élimination de l'eau contenue pour l'obtention d'un gaz sec ;  a PSA waste drying unit compressed by removing the water contained to obtain a dry gas;
une unité ou s'effectue plusieurs étapes successives de condensation/séparation, telle(s) que  a unit or is carried out several successive stages of condensation / separation, such (s) that
‱ chacune des Ă©tapes comprend elle-mĂȘme :  ‱ each of the steps includes itself:
une étape de condensation de tout ou partie du CO2 contenu dans le gaz provenant de l'étape précédente, suivie par  a condensation step of all or part of the CO2 contained in the gas from the previous step, followed by
une Ă©tape de sĂ©paration du condensĂąt riche en CO2 issu de la sĂ©paration d'avec la phase gazeuse contenant les composĂ©s incondensables, Ă©ventuellement par distillation ‱ et, a step of separation of the CO2-rich condensate resulting from the separation from the gas phase containing the incondensable compounds, optionally by distillation ‱ and,
la ou les Ă©tapes sont mises en Ɠuvre Ă  des tempĂ©ratures comprises entre la tempĂ©rature ambiante et -56°C,  the step or steps are carried out at temperatures between room temperature and -56 ° C,
une unité d'appauvrissement en CO2 d'une phase gazeuse issue d'au moins une étape de séparation , par exemple par perméation, pour produire un débit appauvri en CO2 et un débit enrichi en CO2  a CO2 depletion unit of a gaseous phase resulting from at least one separation step, for example by permeation, to produce a depleted flow rate of CO2 and a flow enriched with CO2
une unité de méthanation du débit appauvri en CO2 pour produire un gaz contenant de l'azote et du méthane et  a CO2-depleted flow methanation unit to produce a gas containing nitrogen and methane and
des moyens pour mélanger au moins une partie du flux enrichi en hydrogÚne et au moins une partie du gaz contenant de l'azote et du méthane pour former un gaz de synthÚse d'ammoniac.  means for mixing at least a portion of the hydrogen enriched stream and at least a portion of the nitrogen and methane containing gas to form an ammonia synthesis gas.
L'appareil peut comprendre des moyens pour envoyer le débit enrichi en CO2 provenant de l'étape d'appauvrissement en CO2 à l'unité d'adsorption par modulation de pression.  The apparatus may include means for sending the CO2 enriched flow from the CO2 depletion step to the pressure modulation adsorption unit.
Selon un autre objet de l'invention, il est prévu un appareil de production d'ammoniac et de dioxyde de carbone tel que décrit ci-dessus comprenant une unité de traitement pour traiter le gaz de synthÚse d'ammoniac pour produire un débit d'ammoniac et un gaz contenant du méthane et de l'azote.  According to another object of the invention, there is provided an apparatus for producing ammonia and carbon dioxide as described above comprising a processing unit for treating ammonia synthesis gas to produce a flow rate of ammonia and a gas containing methane and nitrogen.
L'appareil peut comprendre des moyens pour renvoyer le gaz contenant du méthane et de l'azote vers l'étape de reformage.  The apparatus may include means for returning the gas containing methane and nitrogen to the reforming step.
L'appareil peut comprendre une unité de conversion inverse à la vapeur de gaz de synthÚse pour oxyder la majeure partie du monoxyde de carbone qu'elle contient en dioxyde de carbone, avec production correspondante d'hydrogÚne.  The apparatus may include a synthesis gas reverse conversion unit for oxidizing most of the carbon monoxide it contains to carbon dioxide, with corresponding hydrogen production.
L'appareil peut comprendre une unité de reformage du mélange d'hydrocarbures pour l'obtention du gaz de synthÚse contenant au moins du dioxyde de carbone, de l'hydrogÚne, du monoxyde de carbone, du méthane et de la vapeur d'eau.  The apparatus may comprise a reforming unit of the hydrocarbon mixture for obtaining synthesis gas containing at least carbon dioxide, hydrogen, carbon monoxide, methane and water vapor.
L'appareil peut comprendre une unité dans laquelle on fait réagir l'ammoniac avec le dioxyde de carbone pour produire de l'urée.  The apparatus may include a unit in which the ammonia is reacted with the carbon dioxide to produce urea.
La solution selon l'invention consiste Ă  utiliser les gaz incondensables d'un procĂ©dĂ© de production de dioxyde de carbone par sĂ©paration Ă  basse tempĂ©rature pour alimenter une unitĂ© de production de synthĂšse d'ammoniac. Sans Ă©tape de dĂ©carbonatation, mais avec Ă©tape de conversion inverse, le rĂ©sidu du PSA contient une quantitĂ© de CO2 de l'ordre de 45% provenant du reformage et de la conversion inverse (la teneur exacte en CO2 Ă©tant naturellement fonction de la composition du mĂ©lange d'hydrocarbures initial). Le procĂ©dĂ© permet alors, partant du gaz rĂ©siduaire du PSA, dont la pression est typiquement infĂ©rieure Ă  2 bar, de disposer grĂące Ă  la compression d'un gaz Ă  une pression totale comprise entre 40 et 80 bar, correspondant Ă  une pression partielle en CO2 comprise entre 15 et 40 bar, compatible avec la purification cryogĂ©nique. Ces pressions permettront d'utiliser les fluides dans la suite du procĂ©dĂ© sans ĂȘtre obligĂ© de recourir Ă  des compressions supplĂ©mentaires. The solution according to the invention consists in using the incondensable gases of a process for producing carbon dioxide by separation at low temperature to supply an ammonia synthesis production unit. Without decarbonation step, but with reverse conversion step, the PSA residue contains a quantity of CO2 of about 45% from reforming and reverse conversion (the exact content of CO2 is naturally a function of the composition of the mixture initial hydrocarbons). The process then makes it possible, starting from the residual gas of the PSA, whose pressure is typically less than 2 bar, to dispose, thanks to the compression of a gas, at a total pressure of between 40 and 80 bar, corresponding to a partial pressure of CO2. between 15 and 40 bar, compatible with cryogenic purification. These pressures will make it possible to use the fluids in the rest of the process without having to resort to additional compressions.
Le rĂ©siduaire du PSA est donc purifiĂ© par condensation partielle et Ă©ventuellement par permĂ©ation pour produire un dĂ©bit liquide riche en CO2. Ce liquide pourra, grĂące Ă  des traitements complĂ©mentaires appropriĂ©s, ĂȘtre utilisĂ© ou sĂ©questrĂ© sur site ou Ă  proximitĂ© sous forme gazeuse ; il pourra ĂȘtre exportĂ© pour ĂȘtre utilisĂ© ou sĂ©questrĂ© sous forme gazeuse ou liquide. Il pourra notamment et de façon particuliĂšrement avantageuse ĂȘtre utilisĂ© dans l'industrie alimentaire, grĂące Ă  une purification adaptĂ©e.  The PSA waste is purified by partial condensation and optionally by permeation to produce a liquid flow rich in CO2. This liquid can, thanks to appropriate complementary treatments, be used or sequestered on site or nearby in gaseous form; it can be exported for use or sequestered in gaseous or liquid form. It can particularly and particularly advantageously be used in the food industry, through a suitable purification.
En l'absence d'utilisation sur site ou Ă  proximitĂ© du CO2 produit, et selon un premier mode de rĂ©alisation particulier, tout ou partie du liquide est vaporisĂ© aprĂšs dĂ©tente, avec rĂ©cupĂ©ration de froid, pour produire du CO2 sous forme gazeuse sous une pression comprise entre 10 et 35 bar. Le froid rĂ©cupĂ©rĂ© est avantageusement utilisĂ© pour le refroidissement de fluides du procĂ©dĂ© en complĂ©ment des appareils rĂ©frigĂ©rants. Le CO2 pourra ensuite ĂȘtre comprimĂ© pour ĂȘtre transportĂ© par gazoduc sur un site d'utilisation et/ou de sĂ©questration.  In the absence of use on site or in the vicinity of the CO2 produced, and according to a first particular embodiment, all or part of the liquid is vaporized after expansion, with recovery of cold, to produce CO2 in gaseous form under pressure between 10 and 35 bar. The recovered cold is advantageously used for the cooling of process fluids in addition to the refrigerating apparatus. The CO2 can then be compressed to be transported by pipeline to a site of use and / or sequestration.
Selon un autre mode de rĂ©alisation, mais toujours en l'absence d'utilisation sur site ou Ă  proximitĂ© du CO2 produit, tout ou partie du liquide pourrait ĂȘtre transportĂ© sous cette forme sur un site d'utilisation et/ou de sĂ©questration.  According to another embodiment, but still in the absence of use on site or in the vicinity of the CO2 produced, all or part of the liquid could be transported in this form to a site of use and / or sequestration.
Le procĂ©dĂ© est tout particuliĂšrement avantageux lorsqu'il est mis en Ɠuvre pour optimiser la production de gaz de synthĂšse d'ammoniac et produire conjointement du dioxyde de carbone.  The process is particularly advantageous when it is used to optimize the production of ammonia synthesis gas and jointly produce carbon dioxide.
L'invention va maintenant ĂȘtre dĂ©crite en se rĂ©fĂ©rant aux dessins et exemples ci-aprĂšs. Les dessins illustrent des modes de rĂ©alisation particuliers du procĂ©dĂ© de l'invention. The invention will now be described with reference to the drawings and examples hereinafter. The drawings illustrate particular embodiments of the method of the invention.
Il doit ĂȘtre entendu que l'invention ne se limite pas Ă  ces modes de rĂ©alisation. L'homme du mĂ©tier pourra notamment envisager la combinaison des techn iques de traitement et recyclage illustrĂ©s dans ces modes de rĂ©alisation.  It should be understood that the invention is not limited to these embodiments. The person skilled in the art may especially consider the combination of treatment and recycling techniques illustrated in these embodiments.
La Figure 1 représente un diagramme fonctionnel illustrant un mode de réalisation de l'invention pour la production de gaz de synthÚse d'ammoniac et, respectivement, de dioxyde de carbone, par exemple du dioxyde de carbone à séquestrer.  FIG. 1 represents a functional diagram illustrating an embodiment of the invention for the production of synthesis gas of ammonia and, respectively, of carbon dioxide, for example carbon dioxide to be sequestered.
La charge alimentant le procédé est constituée par un mélange d'hydrocarbures - ici du gaz naturel (GN) - le flux 1 d'hydrocarbures alimente une installation 3 comprenant une unité de désulfuration, un pré-reformeur pour produire u n mélange pré-reformé, mélange essentiellement constitué de méthane, d'hydrogÚne, de monoxyde de carbone, de dioxyde de carbone et d'eau, un module de reformage alimenté par le mélange pré-réformé qui produit un gaz de synthÚse contenant essentiellement de l'hydrogÚne, du monoxyde de carbone, du dioxyde de carbone, du méthane et de la vapeur d'eau et un module de conversion inverse.  The feedstock to the process consists of a mixture of hydrocarbons - here natural gas (NG) - the hydrocarbon stream 1 feeds a plant 3 comprising a desulfurization unit, a pre-reformer to produce a pre-reformed mixture, mixture consisting essentially of methane, hydrogen, carbon monoxide, carbon dioxide and water, a reforming module fed by the pre-reformed mixture which produces a synthesis gas substantially containing hydrogen, monoxide of carbon, carbon dioxide, methane and water vapor and a reverse conversion module.
Le gaz de synthĂšse est refroidi puis le gaz refroidi est traitĂ© dans ce module de conversion inverse, oĂč le CO est converti en H2 et en CO2. Le mĂ©lange gazeux 5 sortant de l'installation 3 est refroidi et alors traitĂ© dans une unitĂ© de purification d'hydrogĂšne 7 de type adsorption par modulation de pression ou PSA, pour l'obtention d'un flux gazeux enrichi en hydrogĂšne 9 Ă  une puretĂ© au moins Ă©gale Ă  98% et d'un gaz rĂ©siduaire 1 1 -dit rĂ©siduaire du PSA- contenant le dioxyde de carbone, du mĂ©thane, de l'azote, de l'argon, de l'hydrogĂšne et d u monoxyde de carbone. Ce rĂ©siduaire du PSA 1 1 est disponible Ă  une pression de l'ordre de 1 Ă  3 bar abs, il contient sensiblement tout le CO2 coproduit lors des Ă©tapes de reformage et de conversion inverse. Typiquement, dans le cas de la Figure 1 oĂč le mĂ©lange d'hydrocarbures 1 alimentant le procĂ©dĂ© est du gaz naturel, la composition moyenne du rĂ©siduaire du PSA 1 1 est proche de : CO2 : 45% - CO : 12% - H2 : 23% - CH4 : 17% - H2O : 1 % - N2 : 2%. En tenant compte des variations de composition liĂ©es au cycle de l'unitĂ© PSA, la teneur en CO2 est comprise entre 42 et 48%, la teneur en H2 varie quant Ă  elle entre 20 et 26%, les teneurs des autres constituants restant Ă  peu prĂšs constantes. The synthesis gas is cooled and then the cooled gas is treated in this inverse conversion module, where the CO is converted to H 2 and CO2. The gaseous mixture 5 leaving the plant 3 is cooled and then treated in a hydrogen purification unit 7 of pressure swing adsorption or PSA type, to obtain a gaseous stream enriched with hydrogen 9 at a purity at least equal to 98% and a residue gas 1 1 - waste PSA- containing carbon dioxide, methane, nitrogen, argon, hydrogen and carbon monoxide. This residual PSA 1 1 is available at a pressure of the order of 1 to 3 bar abs, it contains substantially all the CO2 co-produced during the reforming and reverse conversion steps. Typically, in the case of Figure 1 where the mixture of hydrocarbons 1 feeding the process is natural gas, the average composition of the PSA 1 1 waste is close to: CO 2 : 45% - CO: 12% - H2: 23% - CH 4 : 17% - H 2 O: 1% - N 2 : 2%. Taking into account compositional variations related to the cycle of the PSA unit, the CO2 content is between 42 and 48%, the content of H 2 varies between 20 and 26%, the contents of other constituents remaining approximately constant.
Le résiduaire de PSA 1 1 est ensuite épuré dans une unité de purification 13. Le résiduaire du PSA 1 1 est d'abord comprimé dans un module de compression de l'unité de purification, pour l'obtention d'un résiduaire du PSA comprimé. Il est comprimé à 60 bar environ, ce qui assure une pression partielle de CO2 de l'ordre de 27 bar. Ensuite il est débarrassé de ses impuretés lourdes dans un module d'adsorption de l'unité de purification, par une succession d'adsorptions régénérables par exemple, on obtient ainsi un résiduaire comprimé purifié qui est ensuite séché dans un module de séchage de l'unité de purification pour l'obtention d'un résiduaire comprimé, débarrassé des impuretés lourdes et séché.  The PSA residue 1 1 is then purified in a purification unit 13. The PSA 11 1 waste is first compressed in a compression module of the purification unit, to obtain a residual PSA compressed . It is compressed to about 60 bar, which ensures a partial pressure of CO2 of the order of 27 bar. Then it is freed from its heavy impurities in an adsorption module of the purification unit, by a succession of regenerable adsorptions for example, one thus obtains a purified compressed waste which is then dried in a drying module of the purification unit for obtaining a compressed waste, freed from heavy impurities and dried.
Ce rĂ©siduaire est ensuite refroidi pour ĂȘtre sĂ©parĂ© par liquĂ©faction dans un module de sĂ©paration faisant partie de l'unitĂ© de purification , qui permet d'obtenir un liquide 15 contenant essentiellement du CO2 liquide et un mĂ©lange gazeux 17 contenant une fraction de CO2 non condensĂ©e ainsi que les composĂ©s plus lĂ©gers dits incondensables.  This waste is then cooled to be separated by liquefaction in a separation module forming part of the purification unit, which makes it possible to obtain a liquid containing essentially liquid CO2 and a gaseous mixture containing an uncondensed fraction of CO2. than lighter compounds called incondensable.
Le refroidissement du rĂ©siduaire 1 1 est rĂ©alisĂ© par circulation Ă  contre- courant des fluides froids issus de la purification cryogĂ©nique et/ou par Ă©change de chaleur avec un groupe frigorifique extĂ©rieur associĂ©. Le liquide 15 contient essentiellement du CO2, cependant afin d'obtenir du CO2 pur, le liquide 15 rĂ©sulte d'une distillation dans le but de le dĂ©barrasser des impuretĂ©s lĂ©gĂšres entraĂźnĂ©es dans la phase liquide. Pour cela,, le rĂ©siduaire peut ĂȘtre dĂ©tendu Ă  23 bar avant d'alimenter la colonne de distillation .  The cooling of the waste 1 1 is carried out by countercurrent circulation of the cold fluids resulting from the cryogenic purification and / or by heat exchange with an associated external refrigerating unit. The liquid contains essentially CO2, however, in order to obtain pure CO2, the liquid results from a distillation in order to rid it of the light impurities entrained in the liquid phase. For this, the waste can be expanded to 23 bar before feeding the distillation column.
La phase gazeuse 17 obtenue à l'issue de la séparation contient les impuretés légÚres de la charge 1 et se trouve à au moins 40 bars abs ; réchauffée à température ambiante dans les échangeurs de chaleur, elle constitue la purge des incondensables, disponible sous une pression de 58 bar. La composition de la purge est de l'ordre de : CO2 : 21 % - CO : 18% - H2 : 36% - CH4 : 24% - N2 : 1 %. The gas phase 17 obtained at the end of the separation contains the light impurities of the charge 1 and is at least 40 bar abs; warmed to room temperature in the heat exchangers, it is the purge of incondensables, available at a pressure of 58 bar. The composition of the purge is of the order of: CO 2 : 21% - CO: 18% - H 2: 36% - CH 4 : 24% - N 2 : 1%.
La purge des incondensables 17 est alors traitĂ©e dans le module d'adsorption ou de permĂ©ation d'une unitĂ© d'appauvrissement en CO2 19 pour rĂ©duire son contenu en dioxyde de carbone. Un gaz produit 21 a une teneur rĂ©duite en dioxyde de carbone.. L'autre gaz produit 20, enrichi en CO2 et riche en hydrogĂšne, est envoyĂ© Ă  l'unitĂ© PSA 7 pour en amĂ©liorer le rendement, sans ĂȘtre mĂ©langĂ© en amont avec le dĂ©bit 5. The purge of incondensables 17 is then treated in the adsorption or permeation module of a CO2 depletion unit 19 for reduce its carbon dioxide content. A product gas 21 has a reduced content of carbon dioxide. The other product gas 20, enriched in CO2 and rich in hydrogen, is sent to the unit PSA 7 to improve its performance, without being mixed upstream with the flow 5.
En effet, le rendement de l'unitĂ© PSA 7 est trĂšs faible Ă  cause de la forte ten eu r en N 2 , une façon de l'amĂ©liorer est d'introduire le gaz 20 (Ă©ventuellement Ă©tant un permĂ©at), certainement plus riche en H2 que l'alimentation du PSA, au bon moment du cycle, pour amĂ©liorer le rendement du PSA. L'unitĂ© PSA diffĂšre des PSA H2 habituels qui doivent arrĂȘter CO/CO2 et N2. L'unitĂ© 7 arrĂȘter le CO et le CO2, mais peut laisser passer l'azote, ce qui permet de ne pas avoir Ă  se pĂ©naliser sur le rendement H2 de l'unitĂ© PSA 7. In fact, the efficiency of the PSA unit 7 is very low because of the strong hold in N 2, one way of improving it is to introduce the gas (possibly being a permeate), which is certainly richer in H2 that the PSA feed, at the right time of the cycle, to improve the performance of PSA. The PSA unit differs from the usual H 2 PSA that must stop CO / CO 2 and N 2 . The unit 7 stops the CO and the CO2, but can let the nitrogen pass, which makes it possible not to have to penalize itself on the yield H 2 of the unit PSA 7.
Le gaz 21 est ensu ite traité par méthanation dans une unité de méthanation 23 pour transformer les restes de dioxyde de carbone et de monoxyde de carbone en méthane, formant un gaz 25.  The gas 21 is then treated by methanation in a methanation unit 23 to convert the carbon dioxide and carbon monoxide residues into methane, forming a gas.
Le gaz 25 est mélangé avec l'hydrogÚne pur 9 pour former un gaz de synthÚse d'ammoniac 27. Le gaz de synthÚse d'ammoniac 27 est envoyé à une unité 29 de synthÚse d'ammoniac pour produire de l'ammoniac 31 .  The gas is mixed with the pure hydrogen 9 to form an ammonia synthesis gas 27. The ammonia synthesis gas 27 is sent to an ammonia synthesis unit 29 to produce ammonia 31.
L'unité de synthÚse d'ammoniac produit également un gaz 33 contenant du méthane, de l'azote, de l'argon, et de l'hydrogÚne qui est renvoyé à l'unité 3.  The ammonia synthesis unit also produces a gas 33 containing methane, nitrogen, argon, and hydrogen which is returned to unit 3.
Eventuellement l'ammoniac 31 et le dioxyde de carbone 15 peut alimenter une unité de fabrication d'urée 35.  Optionally ammonia 31 and carbon dioxide 15 can feed a urea production unit 35.

Claims

Revendications claims
1 . Procédé pour la production combinée de gaz de synthÚse d'ammoniac et de dioxyde de carbone à partir d'un mélange d'hydrocarbures, comportant au moins : 1. Process for the combined production of synthesis gas of ammonia and carbon dioxide from a mixture of hydrocarbons, comprising at least:
une étape de purification (7) du mélange refroidi issu d'une conversion inverse dans une unité d'adsorption par modulation de pression (ou PSA) permettant l'obtention d'un flux enrichi en hydrogÚne (9) à une pureté au moins égale à 98% et d'un gaz résiduaire (1 1 ) dit « résiduaire du PSA » contenant du dioxyde de carbone, de l'azote, du méthane et du monoxyde de carbone, à une pression de l'ordre de 1 à 3 bar abs,  a purification step (7) of the cooled mixture resulting from an inverse conversion in a pressure modulation adsorption unit (or PSA) allowing a hydrogen-enriched stream (9) to be obtained at a purity of at least equal at 98% and a waste gas (1 1) called "PSA waste" containing carbon dioxide, nitrogen, methane and carbon monoxide, at a pressure of the order of 1 to 3 bar abs,
ainsi qu'une étape de traitement (13) dudit résiduaire du PSA pour l'obtention d'un fluide enrichi en dioxyde de carbone, comportant au moins :  and a treatment step (13) of said PSA waste to obtain a fluid enriched in carbon dioxide, comprising at least:
une étape de compression du résiduaire du PSA jusqu'à une pression supérieure à la pression du reformage et telle que la pression partielle du CO2 contenu soit comprise entre 25 et 35 bar environ ;  a step of compressing the PSA waste to a pressure greater than the reforming pressure and such that the partial pressure of the CO2 content is between about 25 and 35 bar;
une étape de séchage du résiduaire du PSA comprimé par élimination de l'eau contenue pour l'obtention d'un gaz sec ;  a step of drying the compressed PSA waste by removing the water contained to obtain a dry gas;
une étape ou plusieurs étapes successives de condensation/séparation, telle(s) que  a step or several successive stages of condensation / separation, such that
‱ chacune des Ă©tapes comprend elle-mĂȘme :  ‱ each of the steps includes itself:
une étape de condensation de tout ou partie du CO2 contenu dans le gaz provenant de l'étape précédente, suivie par  a condensation step of all or part of the CO2 contained in the gas from the previous step, followed by
une étape de séparation du condensùt riche en CO2 (15) issu de la séparation d 'avec l a ph ase gazeuse (17) contenant les composés incondensables, éventuellement par distillation  a step of separating the CO2-rich condensate (15) resulting from the separation from the gas phase (17) containing the incondensable compounds, optionally by distillation
‱ et,  ‱ and,
- la ou les Ă©tapes sont mises en Ɠuvre Ă  des tempĂ©ratures comprises entre la tempĂ©rature ambiante et -56°C, une Ă©tape d'appauvrissement (19) en CO2 d'une phase gazeuse issue d'au moins une Ă©tape de sĂ©paration, par exemple par permĂ©ation, pour produire un dĂ©bit appauvri en CO2 (21 ) et un dĂ©bit enrichi en CO2 (20) the step or steps are carried out at temperatures between room temperature and -56 ° C, a step of depleting (19) CO2 of a gaseous phase resulting from at least one separation step, for example by permeation, to produce a depleted flow rate of CO2 (21) and a flow rate enriched with CO2 (20)
une étape de méthanation (23) du débit appauvri en CO2 pour produire un gaz contenant de l'azote et du méthane (25) et  a step of methanation (23) of the CO2 depleted flow to produce a gas containing nitrogen and methane (25) and
une étape de mélanger au moins une partie du flux enrichi en hydrogÚne et au moins une partie du gaz contenant de l'azote et du méthane pour former un gaz de synthÚse d'ammoniac (27).  a step of mixing at least a portion of the hydrogen enriched stream and at least a portion of the nitrogen and methane containing gas to form an ammonia synthesis gas (27).
2. Procédé selon la revendication 1 dans lequel le débit appauvri enThe method of claim 1 wherein the depleted flow rate of
CO2 (21 ) est envoyé à la méthanation (23) à une pression d'au moins 35 bars. CO2 (21) is sent to the methanation (23) at a pressure of at least 35 bar.
3. Procédé selon l'une des revendications précédentes dans lequel le débit enrichi en CO2 (20) provenant de l'étape d'appauvrissement en CO2 est envoyé à l'unité d'adsorption par modulation de pression (7). 3. Method according to one of the preceding claims wherein the CO2 enriched flow (20) from the CO2 depletion step is sent to the pressure modulation adsorption unit (7).
4. Procédé selon l'une des revendications précédentes comprenant une étape de conversion inverse à la vapeur (3) de gaz de synthÚse pour oxyder la majeure partie du monoxyde de carbone qu'il contient en dioxyde de carbone, avec production correspondante d'hydrogÚne. 4. Method according to one of the preceding claims comprising a reverse conversion step to the vapor (3) of synthesis gas to oxidize most of the carbon monoxide it contains carbon dioxide, with corresponding production of hydrogen .
5. Procédé selon la revend ication 4 comprenant une étape de reformage (3) du mélange d'hydrocarbures pour l'obtention d'un gaz de synthÚse contenant au moins du dioxyde de carbone, de l'hydrogÚne, du monoxyde de carbone, du méthane, et de la vapeur d'eau. 5. Process according to claim 4 comprising a step of reforming (3) the hydrocarbon mixture to obtain a synthesis gas containing at least carbon dioxide, hydrogen, carbon monoxide, carbon dioxide, methane, and water vapor.
6. Procédé de production d'ammoniac et de dioxyde de carbone selon l'une des revendications précédentes dans lequel on traite le gaz de synthÚse d'ammoniac (27) dans une unité de traitement (29) pour produire un débit d'ammoniac et un gaz contenant du méthane et de l'azote. A method for producing ammonia and carbon dioxide according to one of the preceding claims, wherein the ammonia synthesis gas (27) is treated in a treatment unit (29) to produce a flow of ammonia and a gas containing methane and nitrogen.
7. Procédé selon la revendication dans lequel tout l'azote envoyé à l'unité de synthÚse d'ammoniac (29) provient de la méthanation de la phase gazeuse (17) ou éventuellement du flux enrichi en hydrogÚne. 7. The method of claim wherein all the nitrogen sent to the ammonia synthesis unit (29) comes from the methanation of the gas phase (17) or optionally the hydrogen-enriched stream.
8. Procédé selon la revendication 6 ou 7 dans lequel on renvoie le gaz contenant du méthane et de l'azote (33) vers l'étape de reformage (3). The process of claim 6 or 7 wherein the methane and nitrogen containing gas (33) is returned to the reforming step (3).
9. Procédé de production d'urée selon l'une des revendications précédentes 6, 7 ou 8 dans lequel on fait réagir l'ammoniac (31 )avec le dioxyde de carbone (15) pour produire de l'urée. A process for producing urea according to one of the preceding claims 6, 7 or 8 wherein the ammonia (31) is reacted with the carbon dioxide (15) to produce urea.
10. Appareil pour la production combinée de gaz de synthÚse d'ammoniac et de dioxyde de carbone à partir d'un mélange d'hydrocarbures, comportant au moins : 10. Apparatus for the combined production of syngas of ammonia and carbon dioxide from a mixture of hydrocarbons, comprising at least:
- une unité de purification (7) du mélange refroidi (5) issu d'une conversion inverse dans une unité d'adsorption par modulation de pression (ou PSA) permettant l'obtention d'un flux enrichi en hydrogÚne (9) à une pureté au moins égale à 98% et d'un gaz résiduaire (1 1 ) dit « résiduaire du PSA » contenant du dioxyde de carbone, de l'azote, du méthane et du monoxyde de carbone, à une pression de l'ordre de 1 à 3 bar abs,  - a purification unit (7) of the cooled mixture (5) resulting from an inverse conversion in a pressure modulation adsorption unit (or PSA) making it possible to obtain a stream enriched in hydrogen (9) at a purity of at least 98% and a waste gas (1 1) called "PSA waste" containing carbon dioxide, nitrogen, methane and carbon monoxide, at a pressure in the order of 1 to 3 bar abs,
ainsi qu'une unité de traitement (13) dudit résiduaire du PSA pour l'obtention d'un fluide enrichi en dioxyde de carbone, comportant au moins :  and a processing unit (13) of said PSA waste for obtaining a carbon dioxide-enriched fluid, comprising at least:
une unité de compression du résiduaire du PSA jusqu'à une pression supérieure à la pression du reformage et telle que la pression partielle du CO2 contenu soit comprise entre 25 et 35 bar environ ;  a unit for compressing the PSA waste to a pressure greater than the reforming pressure and such that the partial pressure of the CO2 content is between approximately 25 and 35 bar;
une unité de séchage du résiduaire du PSA comprimé par élimination de l'eau contenue pour l'obtention d'un gaz sec ;  a PSA waste drying unit compressed by removing the water contained to obtain a dry gas;
une unité ou s'effectue une étape ou plusieurs étapes successives de condensation/séparation, telle(s) que  a unit or a step or several successive stages of condensation / separation, such that
· chacune des Ă©tapes comprend elle-mĂȘme :  · Each step includes itself:
une étape de condensation de tout ou partie du CO2 contenu dans le gaz provenant de l'étape précédente, suivie par une étape de séparation du condensùt riche en CO2 issu de la séparation d'avec la phase gazeuse contenant les composés incondensables, éventuellement par distillation a condensation step of all or part of the CO2 contained in the gas from the previous step, followed by a step of separation of the CO2-rich condensate resulting from the separation from the gas phase containing the incondensable compounds, optionally by distillation
‱ et,  ‱ and,
- la ou les Ă©tapes sont mises en Ɠuvre Ă  des tempĂ©ratures comprises entre la tempĂ©rature ambiante et -56°C,  the step or steps are carried out at temperatures between room temperature and -56 ° C,
une unité d'appauvrissement (19) en CO2 d'une phase gazeuse issue d'au moins une étape de séparation, par exemple par perméation, pour produire un débit appauvri en CO2 (21 ) et un débit enrichi en CO2  a CO2 depletion unit (19) of a gaseous phase resulting from at least one separation step, for example by permeation, to produce a depleted flow rate of CO2 (21) and a flow enriched with CO2
- une unité de méthanation (23) du débit appauvri en CO2 pour produire un gaz contenant de l'azote et du méthane (25), et  - a methanation unit (23) of the CO2 depleted flow to produce a gas containing nitrogen and methane (25), and
des moyens pour mélanger au moins une partie du flux enrichi en hydrogÚne et au moins une partie du gaz contenant de l'azote et du méthane pour former un gaz de synthÚse d'ammoniac (27).  means for mixing at least a portion of the hydrogen enriched stream and at least a portion of the nitrogen and methane containing gas to form an ammonia synthesis gas (27).
1 1 . Appareil de production d'ammoniac et de dioxyde de carbone selon la revendication 10 comprenant une unité de traitement (29) pour traiter le gaz de synthÚse d'ammoniac pour produire un débit d'ammoniac (31 ) et un gaz contenant du méthane et de l'azote (33). 1 1. An ammonia and carbon dioxide generating apparatus according to claim 10 comprising a processing unit (29) for treating the ammonia synthesis gas to produce an ammonia flow (31) and a gas containing methane and nitrogen (33).
12. Appareil selon la revendication 10 ou 1 1 comprenant une unité de conversion inverse (3) à la vapeur de tout ou partie du gaz de synthÚse pour oxyder la majeure partie du monoxyde de carbone qu'elle contient en dioxyde de carbone, avec production correspondante d'hydrogÚne. 12. Apparatus according to claim 10 or 1 1 comprising a reverse conversion unit (3) to steam all or part of the synthesis gas to oxidize most of the carbon monoxide it contains carbon dioxide, with production corresponding hydrogen.
13. Appareil selon la revendication 12 comprenant une unité de reformage (3) du mélange d'hydrocarbures (1 ) pour l'obtention d'un gaz de synthÚse contenant au moins du dioxyde de carbone, de l'hydrogÚne, du monoxyde de carbone, du méthane, et de la vapeur d'eau . 13. Apparatus according to claim 12 comprising a reforming unit (3) of the hydrocarbon mixture (1) for obtaining a synthesis gas containing at least carbon dioxide, hydrogen, carbon monoxide , methane, and water vapor.
14. Appareil de production d'urée selon la revendication 1 1 comprenant des moyens pour envoyer le débit d'ammoniac (31 ) et le débit de dioxyde de carbone (15) à une unité de production d'urée (35). A urea production apparatus according to claim 11 comprising means for sending the ammonia flow (31) and the carbon dioxide flow (15) to a urea production unit (35).
EP13733351.4A 2012-06-25 2013-06-06 Method and installation for the combined production of ammonia synthesis gas and carbon dioxide Withdrawn EP2864240A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1256003A FR2992307B1 (en) 2012-06-25 2012-06-25 PROCESS AND INSTALLATION FOR THE COMBINED PRODUCTION OF AMMONIA SYNTHESIS GAS AND CARBON DIOXIDE
PCT/FR2013/051285 WO2014001672A1 (en) 2012-06-25 2013-06-06 Method and installation for the combined production of ammonia synthesis gas and carbon dioxide

Publications (1)

Publication Number Publication Date
EP2864240A1 true EP2864240A1 (en) 2015-04-29

Family

ID=46785669

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13733351.4A Withdrawn EP2864240A1 (en) 2012-06-25 2013-06-06 Method and installation for the combined production of ammonia synthesis gas and carbon dioxide

Country Status (5)

Country Link
US (1) US9206041B2 (en)
EP (1) EP2864240A1 (en)
CN (1) CN104411622A (en)
FR (1) FR2992307B1 (en)
WO (1) WO2014001672A1 (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017184848A1 (en) 2016-04-21 2017-10-26 Fuelcell Energy, Inc. Molten carbonate fuel cell anode exhaust post-processing for carbon dioxide capture
CA3022534C (en) 2016-04-29 2021-01-26 Fuelcell Energy, Inc. Methanation of anode exhaust gas to enhance carbon dioxide capture.
EP3401280B1 (en) * 2017-05-11 2021-12-22 GasConTec GmbH Method for manufacturing ammonium
CN107337178B (en) * 2017-06-05 2020-01-14 ćŽć—ç†ć·„ć€§ć­Š Process for recycling PSA desorption gas and catalytic regeneration flue gas of oil refinery
JP7258144B2 (en) 2018-11-30 2023-04-14 ăƒ•ăƒ„ă‚šăƒ«ă‚»ăƒ« ă‚šăƒŠă‚žăƒŒïŒŒ ă‚€ăƒłă‚łăƒŒăƒăƒŹă‚€ăƒ†ăƒƒăƒ‰ Reforming catalyst pattern for fuel cells operating with enhanced CO2 utilization
WO2021181249A1 (en) * 2020-03-11 2021-09-16 Fuelcell Energy, Inc. Steam methane reforming unit for carbon capture
BR112023005218A2 (en) * 2020-09-21 2023-04-25 Topsoe As IMPROVING THE PURITY OF A CO2-RICH CURRENT
CN113184805A (en) * 2021-04-27 2021-07-30 é™•è„żäžœé‘«ćžŁćŒ–ć·„æœ‰é™èŽŁä»»ć…Źćž Comprehensive utilization and carbon fixation process for pyrolysis gas

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1268428A (en) * 1984-10-22 1990-05-01 John Brian Hansen Johnson Gas separation
US4963339A (en) * 1988-05-04 1990-10-16 The Boc Group, Inc. Hydrogen and carbon dioxide coproduction
FR2877939B1 (en) * 2004-11-16 2007-02-02 Air Liquide PROCESS AND PLANT FOR THE COMBINED PRODUCTION OF HYDROGEN AND CARBON DIOXIDE
KR101304652B1 (en) * 2005-06-06 2013-09-05 레넎 ëŠŹí‚€ë“œ 쏘시에떌 아녞님 ëżŒë„Ž 레드 ì—ë ‰ìŠ€ëż”ëŒë”°ì‹œì˜č 데 í”„ëĄœì„žë° ìĄ°ë„ŽìŠˆ 큮로드 Method for simultaneously producing hydrogen and carbon monoxide
FR2916264A1 (en) * 2006-12-21 2008-11-21 Air Liquide Mixture separating method, involves separating mixture using carbon monoxide cycle, where cycle assures cooling of methane at washing column, over-cooling of washing column and/or condensation at top of denitrification column
US8303930B2 (en) * 2009-05-18 2012-11-06 American Air Liquide, Inc. Processes for the recovery of high purity hydrogen and high purity carbon dioxide
US9321655B2 (en) * 2009-08-20 2016-04-26 Kellogg Brown & Root Llc Systems and methods for producing syngas and products therefrom
US8221524B2 (en) * 2009-10-23 2012-07-17 Guild Associates, Inc. Oxygen removal from contaminated gases
FR2958280A1 (en) 2010-03-30 2011-10-07 Air Liquide PROCESS FOR HYDROGEN PRODUCTION WITH REDUCED CO2 EMISSIONS
FR2961802A1 (en) * 2010-06-29 2011-12-30 Air Liquide Combined production of hydrogen and carbon dioxide from hydrocarbon mixture comprises e.g. reforming hydrocarbon mixture to give synthesis gas, cooling the gas, oxidation reaction, cooling and drying the gas and separating the gas
EP2404869A1 (en) * 2010-07-06 2012-01-11 Ammonia Casale S.A. Process for producing ammonia synthesis gas
US8752390B2 (en) * 2010-07-13 2014-06-17 Air Products And Chemicals, Inc. Method and apparatus for producing power and hydrogen
US8535638B2 (en) * 2010-11-11 2013-09-17 Air Liquide Large Industries U.S. Process for recovering hydrogen and carbon dioxide

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
None *
See also references of WO2014001672A1 *

Also Published As

Publication number Publication date
CN104411622A (en) 2015-03-11
US9206041B2 (en) 2015-12-08
FR2992307A1 (en) 2013-12-27
US20150191351A1 (en) 2015-07-09
WO2014001672A1 (en) 2014-01-03
FR2992307B1 (en) 2014-08-08

Similar Documents

Publication Publication Date Title
EP1814819B1 (en) Method and installation for combined production of hydrogen and carbon dioxide
EP2864240A1 (en) Method and installation for the combined production of ammonia synthesis gas and carbon dioxide
EP3713870B1 (en) Process and device for the combined production of hydrogen and carbon dioxide from a hydrocarbon mixture
CA2888117C (en) Method for producing hydrogen by reforming hydrocarbons using steam, combined with carbon dioxide capture and steam production
EP1890961B1 (en) Method for simultaneously producing hydrogen and carbon monoxide
CA2792012C (en) Method for producing hydrogen with reduced co2 emissions
EP2931654B1 (en) Method for producing hydrogen by reforming hydrocarbons using steam, combined with carbon dioxide capture and steam production
FR2961802A1 (en) Combined production of hydrogen and carbon dioxide from hydrocarbon mixture comprises e.g. reforming hydrocarbon mixture to give synthesis gas, cooling the gas, oxidation reaction, cooling and drying the gas and separating the gas
FR2838424A1 (en) Separation of hydrogen and carbon monoxide from a gas mixture uses a low temperature separation stage for a high purity with simultaneous production without surplus hydrogen
EP4357003A1 (en) Method and apparatus for separating a mixture of hydrogen and carbon dioxide
FR2904780A1 (en) PROCESS FOR SEPARATING A SYNTHESIS GAS CONTAINING HYDROGEN AND CARBON MONOXIDE BUT ALSO AT LEAST CARBON DIOXIDE AND WATER VAPOR
EP1097903B1 (en) Process and apparatus for the production of pure hydrogen starting from a gas containing helium
FR2847568A1 (en) Process and installation for producing a krypton/xenon mixture from air by cryogenic distillation, producing a synthesis gas by partially oxidizing a hydrocarbon and separating the synthesis gas
FR2969134A1 (en) Production and treatment of synthesis gas, by generating synthesis gas by gasification, where synthesis gas contains hydrogen, carbon monoxide, carbon dioxide, methane, water and impurities and purifying acidic impurities washing in column
WO2006042986A1 (en) Method for producing a syngas having a h2/co ratio less than 2.5
FR2671338A1 (en) Process for obtaining a gaseous nitrogen/hydrogen mixture for the synthesis of ammonia
CA3124749A1 (en) Methanol synthsis with co2 recycling and hydrogen separator

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20150126

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

RIC1 Information provided on ipc code assigned before grant

Ipc: C07C 273/10 20060101ALI20170830BHEP

Ipc: B01J 19/24 20060101ALI20170830BHEP

Ipc: C01C 1/04 20060101ALI20170830BHEP

Ipc: C01B 3/56 20060101ALI20170830BHEP

Ipc: C01B 3/02 20060101AFI20170830BHEP

18W Application withdrawn

Effective date: 20170911