Intensification of the Steam Cracking Process Mohamed Ellob, Jonathan Lee, Arthur Gough School of Chemical Engineering and Advanced Materials University of Newcastle Does Steam Cracking Need Steam
Presentation outline Introduction Catalytic plate reactors Coke formation Objectives Benefits Methodology Experimental Work Results Conclusions
Introduction Olefins demand in year 2005 : Ethylene (107 million tons ) propylene (67.1 million tons ) Olefins demand growth during years(2005 2010): Ethylene about 4.3% per year propylene about 5.4% per year Olefins production capacity growth: Ethylene about 5.4% per year Propylene about 5.1% per year
Typical Steam Cracking Furnaces Total Number of cracking tubes about 600 Total Reaction Volume about 45 m³ Total firebox volume about 9,000 m³ Residence Time 0.25 to 0.75 s Firebox Efficiency about 65%
Steam function and process limitation Enhance heat transfer Reduce coke formation and deposition Improve selectivity towards ethylene Operation purposes Coke deposition is the main process limitations due to: - High tube skin temperature - High pressure drop
Exothermic channel gas Exothermic reaction catalyst Heat Thin plate Endothermic channel gas Endothermic reaction catalyst Catalytic Plate Reactor
Source: Velocys,(2005),olefins by high intensity oxidation, http: // www.velocys.com/img/pdf.2250.pdf
Advantages Of Catalytic Plate Reactor High Surface to volume Ratio Laminar flow Conditions High Heat transfer Coefficient Thin Catalyst Layer Minimize Diffusion Limitation Surface Temperature only few degrees above the process temperature Improved Safety and Environmental Impact Scale-up by Numbering up Low Capital and operating Costs
Coke formation Metal-catalyzed coke Non-catalytic coke from tars Small chemical species (coke precursors) react with free radicals on the coke surface Heterogeneous Catalytic Heterogeneous non catalytic Homogeneous non catalytic Chemisorbed HC. Molecule Molecule Radical Coke particle Radical on coke surface Surface reaction Tar droplet
Objectives 1-Study and investigate the possibility of intensifying the thermal cracking of propane to produce ethylene through the use of the catalytic plate reactors. 2- Reducing the coke formation and deposition. 3- Reducing the use of steam. 4- Modelling and simulation for propane cracking using Catalytic Plate Reactor.
Benefits Lower environmental and safety impacts. (NO x, contaminated water, CO 2, H 2 S) Improved energy efficiency. Lower capital cost. Improved overall plant economics
Experimental setup design criteria Allows for accurate coke measurement Constant and uniform temperature along the reactor Very fast cooling of reaction products Easy to change reactor size and material
Nitrogen To CO2 Propane V-1 V-2 Filter-1 FIC-1 V-9 V12 V14 analyser V-3 V-4 Filter-2 FIC-2 PI-1 PI-2 Air V13 Reactor V-5 V-6 Filter-3 FIC-3 Argon V-10 V-7 V-8 Filter-4 FIC-4 Catchpot V15 To GCs Catchpot V16 Propane cracker showing flow paths during decoke Manometer Knock-out V17 Vent
Experimental variables Reactor materials and internal coatings Reactor channel size Process variables ( temperature, pressure, and flow rate) Run time length
Conversion at low and high operating parameters Low flow rate 10 0 95 90 85 80 75 70 Conversion, % 65 60 Temperature low high low high Pressure High flow rate 100 95 90 85 80 75 70 Conversion, % 65 Temperature 60 low high low high Pressure
Coke yield vs Flow at 835 o C and 1.35 bar Coke yield ( mg/g-propane reacted) 1.2 1 0.8 0.6 0.4 0.2 0 1.5 2 2.5 3 3.5 4 4.5 5 Flow, l/h
Coke yield vs Temperature. at 3.5 l/h and 1.35 bar 1.2 Coke yield (mg/g-propane reacted) 1 0.8 0.6 0.4 0.2 810 820 830 840 850 860 Temperature, o C
Coke yield vs Pressure at 3.5 l/h and 835 o C Coke yield (mg/g-propane reacted) 1.1 0.9 0.7 0.5 0.3 0.1 0.9 1 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 Pressure, bar
Coke yield at low and high operating parameters Low flow rate 1.1 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 Coke yield (mg/g-propane reacted) Temperature Low High Low High pressure High flow rate 0.6 0.5 0.4 0.3 0.2 Low Coke yield (mg/g-propane reacted) Temperature High Low High pressure
Inlet of the reactor Middle of the reactor Outlet end of the reactor + Quenching line
UY of Ethylene at low and high operating parameters Low flow rate 50 UY of Ethylene, Weight % 48 46 44 42 40 low Pressure high low High flow rate high Temperature Ultimate Yield = Mass Ethylene Produced Mass Propane In Feed Assuming that the unreacted propane and the ethane produced by one pass through the reactor, are recycled to the feed 50 UY of Ethylene, Weight % 48 46 44 42 40 low Pressure high low high Temperature
Conclusions Conversion of about 90 % can be achieved in 2 mm internal diameter fused silica reactor without any significant pressure drop. Steam use can be reduced or possibly eliminated. High olefins yield can be obtained without steam. Low acetylene and C 4+ yield. Run length of about 14 20 days was estimated to be possible before any decoking is required. This run length was achieved with no steam.
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