DE3816401A1 - Process for purifying raw gas for ammonia synthesis - Google Patents

Process for purifying raw gas for ammonia synthesis

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Publication number
DE3816401A1
DE3816401A1 DE3816401A DE3816401A DE3816401A1 DE 3816401 A1 DE3816401 A1 DE 3816401A1 DE 3816401 A DE3816401 A DE 3816401A DE 3816401 A DE3816401 A DE 3816401A DE 3816401 A1 DE3816401 A1 DE 3816401A1
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DE
Germany
Prior art keywords
raw gas
nitrogen
ammonia synthesis
gas
refrigerant
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Withdrawn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
DE3816401A
Other languages
German (de)
Inventor
Hans Dr Becker
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Linde GmbH
Original Assignee
Linde GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Linde GmbH filed Critical Linde GmbH
Priority to DE3816401A priority Critical patent/DE3816401A1/en
Publication of DE3816401A1 publication Critical patent/DE3816401A1/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • 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
    • 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
    • F25J3/0219—Refinery gas, cracking gas, coke oven gas, gaseous mixtures containing aliphatic unsaturated CnHm or gaseous mixtures of undefined nature
    • 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
    • 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
    • F25J2210/20—H2/N2 mixture, i.e. synthesis gas for or purge gas from ammonia synthesis
    • 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
    • F25J2270/12—External refrigeration with liquid vaporising loop
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/14—External refrigeration with work-producing gas expansion loop
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/42—Quasi-closed internal or closed external nitrogen refrigeration cycle
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/60—Closed external refrigeration cycle with single component refrigerant [SCR], e.g. C1-, C2- or C3-hydrocarbons
    • 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

Abstract

In the process for raw gas purification for ammonia synthesis, the raw gas which has a superstoichiometric nitrogen content is cooled by indirect heat exchange with process streams and subjected to a low-temperature distillation. The additional cold required for cooling the raw gas is generated by means of a refrigerant which is circulated in a closed, separate circuit. Nitrogen is particularly suitable as refrigerant. <IMAGE>

Description

Die vorliegende Erfindung befaßt sich mit einem Verfahren der Reinigung von Rohgas für die Ammoniaksynthese, welches einen überstöchiometrischen Stickstoffgehalt aufweist, durch Tieftemperaturdestillation, bei dem das Rohgas durch indirekten Wärmetausch mit Verfahrensströmen abgekühlt wird, wobei die zur Abkühlung des Rohgases notwendige Zusatzkälte mittels eines Kältemediums erzeugt wird.The present invention relates to a method of Purification of raw gas for ammonia synthesis, which one has superstoichiometric nitrogen content, by Low temperature distillation, in which the raw gas by indirect Heat exchange with process streams is cooled, the to Cooling of the raw gas necessary additional cooling by means of a Refrigerant is generated.

Die Reinigung von Ammoniaksynthesegas kann bekanntermaßen z.B. mittels Stickstoffwäsche oder Tieftemperaturdestillation durchgeführt werden , wobei sich die Wahl der Methode nach dem Verfahren der Synthesegasherstellung richtet.The purification of ammonia synthesis gas is known to be e.g. using nitrogen scrubbing or low-temperature distillation be carried out, the choice of method according to Process of synthesis gas production aimed.

Die Reinigung des Synthesegases wird im besonderen deshalb durchgeführt, um Verunreinigungen daraus zu entfernen, die lhre im System akkumulieren würden, da in der Regel das Produktgas nach der Synthese von nicht umgesetzten Komponenten befreit und diese in den Rohgasstrom zurückgeführt werden. Wie bekannt, hemmen jedoch derartige Verunreinigungen die Umsetzung im katalytischen Reaktor. The cleaning of the synthesis gas is therefore particularly important done to remove contaminants from it, yours would accumulate in the system, as a rule the product gas freed from unreacted components after synthesis and these are returned to the raw gas stream. As known, However, such impurities inhibit the implementation in the catalytic reactor.  

Die europäische Anmeldung EP-A-1 13 530 beschreibt ein Verfahren zur Reinigung von Synthesegas für die Ammoniaksynthese mittels Tieftemperaturdestillation. Getrocknetes Rohgas für die Ammoniaksynthese, welches neben Wasserstoff und Stickstoff im stöchiometrischen Überschuß auch Verunreinigungen wie Methan und Argon enthält, wird im Wärmetausch mit anzuwärmenden Verfahrensströmen abgekühlt und in eine Trennsäule eingespeist. Am Kopf der Trennsäule wird der Stickstoffüberschuß gegen partiell verdampfendes Sumpfprodukt in einem Kopfkondensator kondensiert. Durch die partielle Verdampfung entsteht aus dem Sumpfprodukt eine methanreiche flüssige Fraktion, die zur Kühlung von Rohgas eingesetzt, dabei verdampft und schließlich als Brenngas abgegeben wird, sowie eine stickstoffreiche Gasphase, die ebenfalls gegen Rohgas angewärmt, als Restgas abgegeben wird. Diese stickstoffreiche Gasphase bildet gleichzeitig das Arbeitsmedium für einen offenen Kältekreislauf, bei dem die Kälte durch arbeitsleistende Entspannung in einer Turbine erzeugt wird.European application EP-A-1 13 530 describes a method for the purification of synthesis gas for ammonia synthesis by means of Low temperature distillation. Dried raw gas for the Ammonia synthesis, which in addition to hydrogen and nitrogen in stoichiometric excess also impurities such as methane and Argon contains, is to be heated in the heat exchange Process streams cooled and fed into a separation column. At the top of the separation column, the excess nitrogen is counteracted partially evaporating bottom product in a top condenser condensed. The partial evaporation creates from the Bottom product is a methane-rich liquid fraction that is used for cooling of raw gas, evaporated and ultimately as Fuel gas is released, as well as a nitrogen-rich gas phase, which is also warmed against raw gas and released as residual gas. This nitrogen-rich gas phase also forms that Working medium for an open refrigeration cycle in which the cold is generated by work relaxation in a turbine.

Die Kälteerzeugung auf diese Art ist jedoch nachteilig in Bezug auf ihre thermodynamische Effizienz.The refrigeration in this way is disadvantageous in relation on their thermodynamic efficiency.

Aufgabe der vorliegenden Erfindung ist es, das bekannte Verfahren so auszugestalten, daß der Nachteil des Standes der Technik vermieden wird.The object of the present invention is the known method To be designed so that the disadvantage of the prior art is avoided.

Erfindungsgemäß wird die Lösung dieser Aufgabe dadurch erreicht, daß die Kälteerzeugung durch ein in einem separaten geschlossenen Kältekreislauf geführten Kältemedium erfolgt. According to the invention, this object is achieved by that the refrigeration by a closed in a separate Refrigeration circuit-led refrigerant takes place.  

Durch diese Maßnahme ist der Prozeß der Kälteerzeugung von den übrigen Verfahrensströmen abgekoppelt. Die Erfindung gewährleistet dadurch sowohl die Unabhängigkeit vom zu zerlegenden Gasstrom wie die konstante Zusammensetzung des Wärmetauschmediums in der Anfahrphase.By this measure, the process of refrigeration from the other process streams decoupled. The invention thereby ensures both independence from the decomposing gas flow as the constant composition of the Heat exchange medium in the start-up phase.

Weiterhin wird erfindungsgemäß vorgeschlagen, als Kältemedium Stickstoff zu verwenden.It is also proposed according to the invention as a refrigerant To use nitrogen.

Dies ist in zweierlei Hinsicht von Vorteil. Zum einen findet damit ein Kältemedium Verwendung, welches einen guten Wärmeübergang zum abzukühlenden Rohgas für die Ammoniaksynthese sicherstellt, zum anderen ist es preiswert.This is beneficial in two ways. For one thing thus using a refrigeration medium which is a good one Heat transfer to the raw gas to be cooled for ammonia synthesis secondly, it is inexpensive.

Anhand der Figur sei nun eine Ausführungsform des erfindungsgemäßen Verfahrens beschrieben.Based on the figure, an embodiment of the described method according to the invention.

Ein Rohgasstrom für die Ammoniaksynthese, welcher neben H2 und einem stöchiometrischen Überschuß an N2 die Verunreinigungen CH4, Ar und H2O enthält, wird über Leitung 1 einer Trocknungsanlage 2 zugeführt. Es handelt sich dabei um eine hier nicht näher dargestellte Trocknung mittels Adsorption. Der getrocknete Rohgasstrom 3 wird danach in Wärmetauscher 9 abgekühlt und in eine Trennsäule 4 eingespeist. Die Trennsäule ist durch eine Trennwand und einen Syphon 4 a für den Flüssigkeitsrücklauf in einen am Kopf befindlichen Abscheideraum und in die darunterliegende eigentliche Destillationskolonne unterteilt. Das in einem unteren Bereich zugeführte Rohgas wird durch den stickstoffreichen Rücklauf weitgehend von CH4 und teilweise auch von Ar befreit. Der Rücklauf bildet sich durch Kondensation des Stickstoffüberschusses im Rücklaufkondensator 8. A raw gas stream for the ammonia synthesis, which contains the impurities CH 4 , Ar and H 2 O in addition to H 2 and a stoichiometric excess of N 2 , is fed via line 1 to a drying plant 2 . It is a drying by means of adsorption, not shown here. The dried raw gas stream 3 is then cooled in heat exchanger 9 and fed into a separation column 4 . The separation column is divided by a partition and a siphon 4 a for the liquid return into a separation room located at the top and into the actual distillation column underneath. The raw gas supplied in a lower area is largely freed of CH 4 and partly also of Ar by the nitrogen-rich return. The return line is formed by condensation of the excess nitrogen in the return condenser 8 .

Die entstehende Flüssigkeit wird in den Abscheideraum am Kopf der Destillationskolonne abgetrennt und über den Syphon 4 a der eigentlichen Kolonne zugeführt, während das gereinigte Synthesegas, mit dem für die Ammoniaksynthese notwendigen Stickstoff/Wasserstoff-Verhältnis, über Leitung 11 A abgezogen, im Rohgaskühler 9 gegen Rohgas angewärmt und schließlich über Leitung 11 B der Ammoniaksynthese zugeführt wird. Aus dem Sumpf der Trennsäule wird über Leitung 5 A ein stickstoffreiches Restgas abgezogen, das im Wärmetauscher 6 gegen Kältemedium der Leitung 16 weiter abgekühlt wird. Nach Entspannung in Ventil 7 und Verdampfung und weiterer Erwärmung in dem Rücklaufkondensator 8 und Rohgaskühler 9 wird dieser Strom als Regeneriergas durch die Trocknungsanlage 2 geleitet und beladen mit H2O in Leitung 5 C als Restgas abgegeben.The resulting liquid is separated into the separation chamber at the top of the distillation column and fed to the actual column via the siphon 4 a , while the purified synthesis gas, with the nitrogen / hydrogen ratio necessary for the ammonia synthesis, drawn off via line 11 A , in the raw gas cooler 9 crude gas is heated and finally supplied via line 11 B of the ammonia synthesis. A nitrogen-rich residual gas is drawn off from the bottom of the separating column via line 5 A and is further cooled in the heat exchanger 6 against the cooling medium of line 16 . After relaxation in valve 7 and evaporation and further heating in the reflux condenser 8 and raw gas cooler 9 , this stream is passed as regeneration gas through the drying plant 2 and, loaded with H 2 O in line 5 C, is given off as residual gas.

Um den Kältebedarf der Anlage zu decken, ist sie mit einem geschlossenen Stickstoffkreislauf ausgestattet. In Kompressor 17 verdichteter Stickstoff wird zur Abfuhr der Kompressionswärme gegen Wasser in indirektem Wärmetausch 18 gekühlt und mittels Leitung 12 dem Wärmetauscher 9 zugeführt, wo er zunächst weiter abgekühlt wird. Ein Stickstoffteilstrom wird aus dem Wärmetauscher 9 herausgeführt und zur Kälteerzeugung in der Turbine 15 arbeitsleistend entspannt. Der Reststrom wird im Wärmetauscher 9 weiter abgekühlt und schließlich verflüssigt. Nach der Entspannung im Ventil 13 wird die Verdampfungsenthalpie des Stickstoffs im Wärmetauscher 8 genutzt, um die Kondensationswärme des Rücklaufes für die Destillationskolonne 4 abführen zu können. Der verdampfte Stickstoff verläßt den Wärmetauscher 8 über Leitung 16 und wird in Wärmetauscher 6 genutzt um das Sumpfprodukt der Kolonne 4 vor dessen Entspannung zu unterkühlen. Bevor dieser Stickstoffstrom in Wärmetauscher 9 schließlich wieder auf Umgebungstemperatur angewärmt wird, wird ihm der in Kreislaufturbine 15 entspannte Teilstrom wieder zugemischt.In order to cover the cooling requirements of the system, it is equipped with a closed nitrogen cycle. Nitrogen compressed in the compressor 17 is cooled in indirect heat exchange 18 to remove the heat of compression against water and fed to the heat exchanger 9 by means of line 12 , where it is initially further cooled. A partial nitrogen flow is led out of the heat exchanger 9 and expanded in a work-performing manner to generate cold in the turbine 15 . The residual stream is further cooled in the heat exchanger 9 and finally liquefied. After expansion in the valve 13 , the enthalpy of vaporization of the nitrogen in the heat exchanger 8 is used in order to be able to dissipate the heat of condensation of the reflux for the distillation column 4 . The vaporized nitrogen leaves the heat exchanger 8 via line 16 and is used in the heat exchanger 6 in order to subcool the bottom product of the column 4 before it expands. Before this nitrogen stream in the heat exchanger 9 is finally warmed up again to ambient temperature, the partial stream expanded in the circulation turbine 15 is admixed again.

Claims (2)

1. Verfahren zur Reinigung von Rohgas für die Ammoniaksynthese, welches einen überstöchiometrischen Stickstoffgehalt aufweist, durch Tieftemperaturdestillation, bei dem das Rohgas durch indirekten Wärmetausch mit Verfahrensströmen abgekühlt wird, wobei die zur Abkühlung des Rohgases notwendige Zusatzkälte mittels eines Kältemediums erzeugt wird, dadurch gekennzeichnet, daß die Kälteerzeugung durch ein in einem separaten, geschlossenen Kältekreislauf geführten Kältemedium erfolgt.1. A process for the purification of raw gas for ammonia synthesis, which has an over-stoichiometric nitrogen content, by low-temperature distillation, in which the raw gas is cooled by indirect heat exchange with process streams, the additional cooling required for cooling the raw gas being generated by means of a cooling medium, characterized in that the refrigeration is carried out by a refrigerant in a separate, closed refrigeration cycle. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als Kältemedium Stickstoff verwendet wird.2. The method according to claim 1, characterized in that as Refrigerant nitrogen is used.
DE3816401A 1988-05-13 1988-05-13 Process for purifying raw gas for ammonia synthesis Withdrawn DE3816401A1 (en)

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Application Number Priority Date Filing Date Title
DE3816401A DE3816401A1 (en) 1988-05-13 1988-05-13 Process for purifying raw gas for ammonia synthesis

Applications Claiming Priority (1)

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DE3816401A DE3816401A1 (en) 1988-05-13 1988-05-13 Process for purifying raw gas for ammonia synthesis

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DE3816401A1 true DE3816401A1 (en) 1989-11-16

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DE3816401A Withdrawn DE3816401A1 (en) 1988-05-13 1988-05-13 Process for purifying raw gas for ammonia synthesis

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2292554A1 (en) * 2009-09-02 2011-03-09 Ammonia Casale S.A. Production of ammonia make-up syngas with cryogenic purification
CN104556145A (en) * 2014-12-31 2015-04-29 贵州天福化工有限责任公司 Advanced heating system for ammonia synthesis catalyst and heating method

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2292554A1 (en) * 2009-09-02 2011-03-09 Ammonia Casale S.A. Production of ammonia make-up syngas with cryogenic purification
WO2011026771A1 (en) * 2009-09-02 2011-03-10 Ammonia Casale Sa Production of ammonia make-up syngas with cryogenic purification
US10273155B2 (en) 2009-09-02 2019-04-30 Casale Sa Production of ammonia make-up syngas with cryogenic purification
CN104556145A (en) * 2014-12-31 2015-04-29 贵州天福化工有限责任公司 Advanced heating system for ammonia synthesis catalyst and heating method

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