DE3101067A1 - "Process for generating ammonia synthesis gas according to the steam-reforming process" - Google Patents
"Process for generating ammonia synthesis gas according to the steam-reforming process"Info
- Publication number
- DE3101067A1 DE3101067A1 DE19813101067 DE3101067A DE3101067A1 DE 3101067 A1 DE3101067 A1 DE 3101067A1 DE 19813101067 DE19813101067 DE 19813101067 DE 3101067 A DE3101067 A DE 3101067A DE 3101067 A1 DE3101067 A1 DE 3101067A1
- Authority
- DE
- Germany
- Prior art keywords
- gas
- ammonia synthesis
- synthesis gas
- furnace
- steam
- 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- Withdrawn
Links
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 16
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 15
- 238000000629 steam reforming Methods 0.000 title claims description 4
- 239000007789 gas Substances 0.000 claims abstract description 56
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 13
- 239000000571 coke Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 239000003345 natural gas Substances 0.000 claims description 3
- 239000003915 liquefied petroleum gas Substances 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 description 11
- 239000000126 substance Substances 0.000 description 7
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000004868 gas analysis Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Industrial Gases (AREA)
Abstract
Description
"Verfahren zur Erzeugung von Ammoniak-Synthesegas nach"Process for the production of ammonia synthesis gas according to
dem Steam-Reforming-Prozeß" Die Erfindung betrifft ein Verfahren nach dem Oberbegriff des Anspruchs 1. the steam reforming process "The invention relates to a method according to the preamble of claim 1.
Solche konventionelle Verfahren zur Erzeugung von Ammoniak-Synthesegas arbeiten in der Weise, daß der Einsatzstoff, wie Kokereigas, Erdgas, Raffineriegas, Flüssiggas oder Naphtha in einem Röhrenspaltofen mit Wasserdampf bei Reaktionstemperaturen zwischen 750 und 900° sowie Reaktionsdrücken bis zu 35 bar zu Spaltgas umgesetzt wird. Die Einstellung des Wasserstoff/Stickstoff-Verhältnisses erfolgt in einem nachfolgenden autothermen Reaktor, der bei Reaktionstemperaturen zwischen 900 und 11000 C arbeitet. In diesem Reaktor wird mittels Luft das Spaltgas weiter katalytisch durchgespalten; gleichzeitig wird über den Stickstoffanteil der Luft das erforderliche Wasserstoff/Stickstoff-Verhältnis des Ammoniak-Synthesegases eingestellt. In den folgenden Prozeßstufen: Normalkonvertierung, Tieftemperaturkonvertierung, C02-Wäsche, Methanisierung wird Kohlenmonoxyd weitestgehend zu Wasserstoff umgesetzt, das Kohlendioxyd ausgewaschen sowie die Spuren von CO und C02, die ftir die nachfolgende Ammoniak-Synthese Katalysatorgifte darstellen, zu Methan umgeformt.Such conventional methods of producing ammonia synthesis gas work in such a way that the feedstock, such as coke oven gas, natural gas, refinery gas, Liquid gas or naphtha in a tubular fission furnace with steam at reaction temperatures between 750 and 900 ° and reaction pressures up to 35 bar converted to cracked gas will. The setting of the hydrogen / nitrogen ratio takes place in one subsequent autothermal reactor, which operates at reaction temperatures between 900 and 11000 C works. In this reactor, the cracked gas becomes further catalytic by means of air split through; at the same time, the nitrogen content of the air increases the amount required Hydrogen / nitrogen ratio of the ammonia synthesis gas set. In the following process stages: normal conversion, low temperature conversion, C02 washing, Methanation, carbon monoxide is largely converted into hydrogen, the carbon dioxide washed out as well as the traces of CO and CO 2, which are necessary for the subsequent ammonia synthesis Represent catalyst poisons, transformed into methane.
Die Erfindung hat sich eine Vereinfachung und Verbilligung der Verfahrensführung und Verringerung der Investitionskosten gegenüber dem zuvor beschriebenen konventionellen Ammoniak-Synthesegas-Prozeß zum Ziel gesetzt.The invention has a simplification and cheaper process management and a reduction in investment costs over the conventional one described above Aimed at ammonia synthesis gas process.
Dieses Ziel wird erreicht durch die Zugabe von Hochofengichtgas als Stickstoffträger. Dadurch, daß der erforderliche Stickstoffanteil für das Ammoniak-Synthesegas nicht über Prozeßluft, sondern über Hochofengichtgas eingebracht wird, kann auf den autothermen Reaktor, der üblicherweise dem Röhrenofen nachgeschaltet ist, verzichtet werden.This goal is achieved by adding blast furnace top gas as Nitrogen carriers. Because the required nitrogen content for the ammonia synthesis gas is not introduced via process air, but via blast furnace top gas, can on the autothermal reactor, which is usually located downstream of the tube furnace, is dispensed with will.
Ein weiterer Vorteil dieser Erfindung liegt darin, daß die maximale Prozeßgastemperatur 100-2000 (autothermer Reaktor) niedriger liegt, was Einfluß auf die Materia7kosten haben wird. Auch das erfindungsgemäße Verfahren eignet sich gleichermaßen für Einsatzstoffe wie Koksofengas, Erdgas, Raffineriegas, Flüssiggas und Naphtha.Another advantage of this invention is that the maximum Process gas temperature 100-2000 (autothermal reactor) is lower, what influence on the material costs. The method according to the invention is also suitable equally for input materials such as coke oven gas, natural gas, refinery gas, liquid gas and naphtha.
Wird das Prozeßgichtgas gemäß Anspruch 2 vor der Konvertierung dem Spaltgas zugemischt, so hat diese Prozeßführung den Vorteil, daß der Gaserzeugungsanlagenteil mit den dazugehörenden Wärmeaustauschern kleiner dimensioniert werden kann als im Falle der konventionellen Ammoniak-Synthesegaserzeugung, bei der der Stickstoff über die Luft dem autothermen Reaktor und damit dem Prozeß zugeführt werden muß.If the process furnace gas according to claim 2 before the conversion If cracked gas is mixed in, this process control has the advantage that the gas generation system part with the associated heat exchangers can be dimensioned smaller than in Case of conventional ammonia synthesis gas production, in which the nitrogen must be supplied via the air to the autothermal reactor and thus to the process.
Nachfolgend wird anhand der beiliegenden Zeichnung ein Beispiel für die Ausführung des erfindungsgemäßen Verfahrens mit Koksofengas als Einsatzstoff näher erläutert.An example for the implementation of the method according to the invention with coke oven gas as the feedstock explained in more detail.
Das Koksofengas a wird verdichtet und einer Entschwefelungsstufe 1 zugeführt. Nach der Entschwefelung wird das Koksofengas vorgewärmt. Nach Zumischung von Wasserdampf, der in Abhitzekesseln eines Röhrenofens 2 erzeugt wird, wird das Koksofengas katalytisch im Röhrenspaltofen 2 umgesetzt. Der Röhrenofen 2 wird zweckmäßigerweise mit Koksofengas d und Lösungs-und Entspannungsgas c aus der Ammoniak-Synthese-Stufe 6 unter Verwendung von Verbrenrlullgnluft t unterfeuert.The coke oven gas a is compressed and subjected to a desulfurization stage 1 fed. After desulfurization, the coke oven gas is preheated. After admixture of water vapor that is generated in the waste heat boilers of a tube furnace 2, that Coke oven gas reacted catalytically in the tube furnace 2. The tube furnace 2 is expediently with coke oven gas d and solution and expansion gas c from the ammonia synthesis stage 6 underfired using combustion air t.
Gichtgas c wird verdichtet und entschwefelt, bevor es bei f vor der Konvertierungsstufe 3 dem Spaltgas aus dem Röhrenofen 2 zugesetzt wird. Es ist auch möglich, das Gichtgas bei f' oder f'', also schon vor der Verdichtung und Entschwefelung bzw. vor dem Spaltofen 2 dem Prozeß zuzuführen. Die Zuführung des Gichtgases bei f" hätte den Vorteil, daß eine separate Entschwefelung sowie der Gichtgaskompressor entfallen kann.Blast furnace gas c is compressed and desulphurized before it is before the at f Conversion stage 3 is added to the cracked gas from the tube furnace 2. It is also possible, the furnace gas at f 'or f' ', i.e. before compression and desulfurization or upstream of the cracking furnace 2 to be supplied to the process. The supply of the furnace gas at f "would have the advantage that a separate desulfurization and the top gas compressor can be omitted.
Die Menge des Gichtgases c wird durch das erforderliche Wasserstoff/Stickstoff-Verhältnis bestimmt. Die nachfolgenden Prozeßstufen: Konvertierung 3, CO2-Wäsche 4, Methanisierung 5 sind wie bei der konventionellen Ammoniäk-Synthesegaserzeugung auch hier erforderlich.The amount of furnace gas c is determined by the required hydrogen / nitrogen ratio certainly. The following process stages: conversion 3, CO2 scrubbing 4, methanation 5 are required here, as in conventional ammonia synthesis gas generation.
In der Zeichnung bedeuten ferner 6 die Ammoniak-Synthese-Stufe, b das erzeugte Ammoniak und g das CO2-Abgas.In the drawing, 6 also denote the ammonia synthesis stage, b the ammonia produced and g the CO2 exhaust gas.
Das nachfolgende Beispiel basiert auf dem Einsatzstoff Koksofengas und soll typische Mengenverhältnisse sowie Betriebsparameter deutlich machen.The following example is based on the raw material coke oven gas and should make typical proportions and operating parameters clear.
Beispiel: 1. Eintritt Röhrenspaltofen (nach Entschwefelung) Analyse Koksofengas Stoff Vol t (trocken) Schwefelgehalt 1 ppm CO2 0,62 CO 6,03 H2 63,48 25,75 C2H6 1,00 N2 3,12 100,00 Gasmenge: 1060 mn³ (trocken) Wasserdampf-Zugabe: 2540,0 mn³ Temperatur Koksofengas: 450 C Temperatur-Dampf: 4500 C Druck der Reaktionsmedien: 24 bar 2. Austritt Röhrenspaltofen Analyse Spaltgas Stoff Vol % (trocken) CO2 8,35 CO 8,68 H2 80,65 CH4 0,53 N2 1,59 100,00 Reaktionsdruck = 20,0 bar Reaktionstemperatur = 875,00 C Spaitgasmenge = 20 mn3 (trocken) Wasserdampf-Menge 2100 mn³ 3. Mischung Spaltgas + Gichtgas Gichtgasanalyse: Stoff Vol 8 (trocken) Druck: 22 bar CO2 15,00 Temperatur: 200 C (360° C) CO 25,00 H2 4,00 N2 56,00 - 100,00 Gichtgasmenge: 1450 m Analyse nach Mischung Stoff Vol % trocken CO2 10,74 CO 14,54 H2 53,26 CH4 0,34 N2 21,12 - 100,00 Gasmenge zur Konvertierung 3210 in (trocken) Wasserdampf im Mischgas zur Konvertierung Od#O mn3 4. Konvertierung Konvertgasanalyse. Austritt Tieftemperaturkonvertierung Stoff Vol % (trocken) Druck: 17 bar Co2 2i,83 Temperatur: 2400 C CO 0,30 H2 59,08 CH4 0,30 N2 18,49 100,00 Konvertgas Austritt 3670 m (trocken) n Wasserdampf im Konvertgas 1640 5. CO2 -Wäsche Gasanalyse Austritt: Stoff Vol % (trocken) Druck: 16 bar CO2 0,10 Temperatur: 80°C CO 0,38 H2 75,00 CH4 0,38 N2 24,14 100,00 Gereinigtes Gas Austritt 2870 mn³ (trocken) C03-Abqas: 800 m³ (trocken) Druck: 1 bar abs Temperatur: 600 C 6. Synthesegas (nach Methanisierung) Gasanalyse: Stoff Vol t (trocken) Druck: 15,5 bar CO2 10 ppm CO ) * H2 74,70 CH4 0,87 N2 24,43 - 100,00 Synthesegasmenge 2g30 (trocken)Example: 1. Entry into the tube gap furnace (after desulfurization) analysis Coke oven gas substance Vol t (dry) Sulfur content 1 ppm CO2 0.62 CO 6.03 H2 63.48 25.75 C2H6 1.00 N2 3.12 100.00 Amount of gas: 1060 mn³ (dry) Water vapor addition: 2540.0 mn³ Coke oven gas temperature: 450 C Steam temperature: 4500 C Pressure of the reaction media: 24 bar 2nd outlet tube cracking furnace Analysis cracking gas substance Vol% (dry) CO2 8.35 CO 8.68 H2 80.65 CH4 0.53 N2 1.59 100.00 reaction pressure = 20.0 bar reaction temperature = 875.00 C amount of hot gas = 20 mn3 (dry) amount of water vapor 2100 mn³ 3. Mixture of cracked gas + furnace gas furnace gas analysis: substance Vol 8 (dry) pressure: 22 bar CO2 15.00 Temperature: 200 C (360 ° C) CO 25.00 H2 4.00 N2 56.00 - 100.00 Top gas quantity: 1450 m analysis according to mixture substance vol% dry CO2 10.74 CO 14.54 H2 53.26 CH4 0.34 N2 21.12 - 100.00 Amount of gas for converting 3210 into (dry) water vapor in the mixed gas for conversion Od # O mn3 4. Conversion convert gas analysis. Outlet low temperature conversion substance vol% (dry) pressure: 17 bar Co2 2i, 83 Temperature: 2400 C CO 0.30 H2 59.08 CH4 0.30 N2 18.49 100.00 Convert gas outlet 3670 m (dry) n Water vapor in the converting gas 1640 5. CO2 scrubbing Gas analysis outlet: Substance% by volume (dry) Pressure: 16 bar CO2 0.10 Temperature: 80 ° C CO 0.38 H2 75.00 CH4 0.38 N2 24.14 100.00 Purified gas outlet 2870 mn³ (dry) C03 waste gas: 800 m³ (dry) pressure: 1 bar abs temperature: 600 C 6. Synthesis gas (according to Methanation) Gas analysis: substance vol t (dry) pressure: 15.5 bar CO2 10 ppm CO ) * H2 74.70 CH4 0.87 N2 24.43 - 100.00 Synthesis gas quantity 2g30 (dry)
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19813101067 DE3101067A1 (en) | 1981-01-15 | 1981-01-15 | "Process for generating ammonia synthesis gas according to the steam-reforming process" |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19813101067 DE3101067A1 (en) | 1981-01-15 | 1981-01-15 | "Process for generating ammonia synthesis gas according to the steam-reforming process" |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE3101067A1 true DE3101067A1 (en) | 1982-07-22 |
Family
ID=6122662
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19813101067 Withdrawn DE3101067A1 (en) | 1981-01-15 | 1981-01-15 | "Process for generating ammonia synthesis gas according to the steam-reforming process" |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE3101067A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4988490A (en) * | 1988-09-14 | 1991-01-29 | Air Products And Chemicals, Inc. | Adsorptive process for recovering nitrogen from flue gas |
| US20160348196A1 (en) * | 2013-12-12 | 2016-12-01 | Thyssenkrupp Ag | Method for generating synthesis gas in conjunction with a smelting works |
| US20170210703A1 (en) * | 2013-12-12 | 2017-07-27 | Thyssenkrupp Ag | Method for preparation of ammonia gas and co2 for a urea synthesis process |
-
1981
- 1981-01-15 DE DE19813101067 patent/DE3101067A1/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4988490A (en) * | 1988-09-14 | 1991-01-29 | Air Products And Chemicals, Inc. | Adsorptive process for recovering nitrogen from flue gas |
| US20160348196A1 (en) * | 2013-12-12 | 2016-12-01 | Thyssenkrupp Ag | Method for generating synthesis gas in conjunction with a smelting works |
| US20170210703A1 (en) * | 2013-12-12 | 2017-07-27 | Thyssenkrupp Ag | Method for preparation of ammonia gas and co2 for a urea synthesis process |
| US10519102B2 (en) | 2013-12-12 | 2019-12-31 | Thyssenkrupp Ag | Method for preparation of ammonia gas and CO2 for a urea synthesis process |
| US10697032B2 (en) * | 2013-12-12 | 2020-06-30 | Thyssenkrupp Ag | Method for generating synthesis gas in conjunction with a smelting works |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| OP8 | Request for examination as to paragraph 44 patent law | ||
| 8130 | Withdrawal |