Thyssenkrupp Ag · XETR:TKA
Thyssenkrupp — Uhde — Nitrogen + Syngas Conference 2010
22 slides from Thyssenkrupp's conference presentation, Mar 1, 2010
Slide 1: Autothermal reforming: a flexible syngas route with future potential
Autothermal reforming: a flexible syngas route with future potential Dr. Klaus Noelker, Dr. Joachim Johanning, Uhde GmbH Nitrogen + Syngas Conference, Bahrain 1 – 3 March 2010
Slide 2: Synthesis gas and its generation
Synthesis gas and its generation Gas mixture of H2 and CO Basis for important processes such as synthesis of ammonia, methanol, ... Syngas generation: Feedstock Syngas generator Product external heating: natural gas, steam reformer methanol naphtha internal heating: synthesis gas (H2 + CO) NH3 natur
Slide 3: Synthesis gas and its generation
Synthesis gas and its generation Main chemical reactions for synthesis gas generation by autothermal reforming of CH4: Steam reforming of CH4: CH4 + H2O → CO + 3 H2 ∆HR = +206 kJ/mol endothermal Partial oxidation: CH4 + ½ O2 → CO + 2 H2 ∆HR = -35 kJ/mol exothermal 3
Slide 4: Synthesis gas composition
Synthesis gas composition Synthesis gas composition requirements (outlet reformer): ammonia: (H2 + CO) / N2 ≈ 3.0 methanol: (H2 – CO2) / (CO + CO2) ≈ 2.0 hydrogen: H2 = max. gas to liquids: H2 / CO ≈ 2.0 Composition ranges provided: steam reformer combined reforming 1) ATR 1) POX reactor Note 1) pos
Slide 5: Application of autothermal reforming
Application of autothermal reforming Autothermal reforming already established for syngas production: stand-alone ATR for GTL plants ATR combined with conventional tubular primary reformer for NH3 and methanol plants: – NH3: ATR used as secondary “mild” conditions by: reformer on pre-reformed gas –
Slide 6: Flowsheet options for ATR based NH3 plant
Flowsheet options for ATR based NH3 plant Different oxidator compositions possible ⇒ different flowsheets for syngas generation of an NH3 plant possible Oxidator Oxygen demand Nitrogen content compared to demand of NH3 synthesis plain air too high (21 % O2) defined by heat enriched air demand of the
Slide 7: Flowsheet options for ATR based NH3 plant: Option 1
Flowsheet options for ATR based NH3 plant Option 1: Plain air as oxidator air steam steam natural ATR gas CO CO2 cold NH3 gas cooling conv. removal box synth. waste gas Gas composition: large N2 surplus in syngas Consequence: either cryogenic unit to remove N2 or large purge gas stream Size: largest
Slide 8: Flowsheet options for ATR based NH3 plant: Option 2
Flowsheet options for ATR based NH3 plant Option 2: Oxygen enriched air as oxidator steam steam natural ATR gas CO CO2 metha- NH3 gas cooling conv. removal nation synth. oxygen + nitrogen air air sep. purge plant treatm. Gas composition: correct amount of N2 for NH3 synthesis Consequence: need air s
Slide 9: Flowsheet options for ATR based NH3 plant: Option 3
Flowsheet options for ATR based NH3 plant Option 3: Pure oxygen as oxidator liquid nitrogen steam steam wash unit natural ATR gas CO CO2 LN NH3 gas cooling conv. removal wash synth. oxygen liquid nitrogen air air sep. plant Gas composition: no N2 in syngas Consequence: N2 to be added at the end of t
Slide 10: Economic comparison between 3 options
Flowsheet options for ATR based NH3 plant Economic comparison between 3 options Operating cost: Similar (similar energy consumption) Investment cost: Option 3 (pure oxygen) seems to be most expensive: – large air separation unit – nitrogen wash unit 10
Slide 11: Economic comparison between steam reformer and ATR plant
Economic comparison between steam reformer and ATR plant Operating cost (energy consumption) steam reformer ATR basis heat of reaction supplied by burning feed gas ⇒ higher feed gas flow ⇒ higher energy demand for preheating lower loss from flue gas air separation Overall: + 6 % cost for option “enr
Slide 12: Economic comparison between steam reformer and ATR plant
Economic comparison between steam reformer and ATR plant Investment cost judgement difficult because no purely on ATR based NH3 plant built so far steam reformer ATR basis air separation biggest contributors no steam reformer ~ ATR similar to secondary reformer liquid nitrogen wash unit (option “pur
Slide 13: Relative investment cost
Economic comparison between steam reformer and ATR plant Investment cost Most significant effect comes from cost relation of air separation and steam reformer steam reformer: cost relative investment cost almost linear with capacity (no significant “economy of scale”) cost range of air separation un
Slide 14: Uhde's ATR test facility – process flow diagram
Uhde’s ATR test facility – process flow diagram Hydrogen Nitrogen feed / steam Oxygen supply oxidator supply Natural gas Propane Steam cooling circuit for nozzles syngas output: reactor max. 1000 Nm3/h to flare Syngas Quench water inlet Quench water outlet 14
Slide 15: Uhde's ATR test facility
Uhde’s ATR test facility A us Datenschutzgründen wurde das automatische Herunterladen dieses Bilds v on PowerPoint gesperrt. 15
Slide 16: Uhde's ATR test facility
Uhde’s ATR test facility 2007 – 2009: Installation of test facility in Russia in an existing chemical complex – advantage: all utilities and manpower available June 2009: first ignition Highlights: Critical parameter: soot formation at low steam-to-carbon ratio of the feed gas Sampling nozzles for s
Slide 17: Test programme for the ATR
Test programme for the ATR Outlet gas requirements: composition (e.g. [CO + H2] / N2 ≈ 3.0 or H2 : CO ≈ 2.0; no soot) Design parameters: Operating parameters: combustion zone geometry, nozzles etc. steam-to-carbon ratio combustion zone gas residence time combustion zone temperature inlet velocity fe
Slide 18: Test programme for the ATR
Test programme for the ATR Variation of parameters: Parameter Unit Lower Upper limit limit feedstock higher hydrocarbon content % 2 14 N2 content oxidator % 0 55 operating pressure bar 20 30 steam-to-carbon ratio – 0.5 3.0 combustion zone shape – A B rel. gas residence time comb. zone % 50 100 combu
Slide 19: Operational results from the ATR test facility (1)
Operational results from the ATR test facility (1) Operation without catalyst Operating point A B C Parameter Unit NH3 NH3 FT syngas, syngas, syngas enriched pure air oxygen Feed CH4 content % mole 89.2 82.9 88.7 Feed C2+ content % mole 7.1 14.5 7.4 Oxidator N2 content % mole 42.1 5.0 5.0 Steam-to-c
Slide 20: Operational results from the ATR test facility (2)
Operational results from the ATR test facility (2) Operation with catalyst, p = 28 bar Operating point A B C Parameter Unit NH3 NH3 FT syngas, syngas, syngas enriched pure air oxygen Feed CH4 content % mole 91.9 91.3 96.9 Feed C2+ content % mole 4.0 4.8 1.9 Oxidator N2 content % mole 48.9 5.0 5.0 St
Slide 21: Summary
Summary Autothermal reformers well established in combination with other syngas generators like tubular reformers (“conventional concept”) Cost advantage of conventional concept vs. stand-alone ATR shrinking at higher plant capacity Research work triggered by less experience with stand-alone ATR Uhd
Slide 22: Thank you for your attention!
Summary Thank you for your attention! Questions please! 22