Potentials for Ultra-clean Fuels Obtained from Natural Gas via GTL to Play a Role in Aviation and Automotive Industry Nimir O. Elbashir Texas A&M University at Qatar MEDW 2013 & Petchem Arabia Conferences May 14, 2013; Sofitel Hotel, Abu Dhabi, UAE
Content Qatar leading role in Gas Processing Technologies. Gas-to-Liquid technology and its potentials. Commercial Fischer-Tropsch (FT) technologies Enhancement in FT reactor and processing design to enhance ultra clean fuels production. Synthetic jet fuels from GTL, the potentials and the challenges. 2
Potentials for natural gas to play a major role in the Energy Market Total Reserve 6,607 tcf Total Primary Energy: 4 EJ/year Malaysia Indonesia Oil Gas Coal Hydro Nuclear Renewable Venezuela Algeria United Arab Qatar Russia 0 10 20 30 3
Qatar contribution to the Energy Market Pipeline Total Primary Energy: 4 EJ/year LNG Oil Gas Coal Hydro Nuclear Renewable Natural Gas Physical 1/600 volume GTL Qatar s aspiration to become the World Gas Capital led to the building the largest GTL and LNG plants in the world. 4
Dolfin Gas Project QatarGas Project Shell the Pearl GTL Plant ExxonMobil Support LNG Facilities 5
Crude Oil Vs. Natural Gas ($/MMBTU) 6
Natural Gas Production 7
LNG vs. GTL, which option is better? From Mike Nel (Sasol) Presentation at the XTL World Summit in London June 2011. 8
Fuels transportation - Major producers and users are located at great distances from each other. - Fuels must be transported great distances. - Due to transportation concerns, liquid fuels are favored. Major trade movements 2009 (Millions of tons) [BP Statistical Review of world energy 2010] 9
Synthetic Fuels Have Bright Future! Obtained from SHELL Global Solution, 2007. Cherillo, et al. Verification of Shell GTL Fuel as CARB Alternative Diesel
GTL fuels environmentally attractive Extremely low (0-5-ppm) sulfur, aromatics, and toxics
Natural Gas Coal Gas-to-Liquid Technology: Alternative Energy Supply & Source of Value-Added Chemicals Synthesis Gas Production Syngas H 2 /CO Fischer-Tropsch Lights HC (Feedstock) Liquid Fuels Biomass HC Wax Lubricants Flexibility in feedstock's Large product distributions Ultra clean fuels (high cetane number and low sulfur content diesel + low octane gasoline) & value added chemicals 12
Fischer-Tropsch chemistry facilitates the conversion of syngas into liquids α-olefins+ Gasoline + Jet Fuel+ Diesel +wax C n H 2n and C n H 2n+2 + CO 2, H 2 O, oxygenates H 2 CO H H H C O Catalyst Surface: Cobalt, Iron, Ruthenium, etc 13 O H
Hydrocarbon wt% Selective control of hydrocarbon product distribution 12 10 8 Gasoline Jet Fuels Diesel Wax 6 4 2 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Carbon Number
GTL technology in Qatar 1 million tons of kerosene/ year + base oil 24,000 bpd diesel + 9,000 bpd naphtha +1,000 bpd LPG 15
Comparison between FTS reactors Desired Characteristics Operational Consideration Packed bed reactor (gas phase) Slurry phase reactor (liquid phase) High Catalyst hold-up The ideal FTS reactor should combine the advantages of the two major reactor High technologies; reactor fixed-bed productivity reactors of high reactant diffusivity and reaction rates coupled with steady performance to that of the slurry reactor of well-mixed phase and Easy excellent catalyst temperature separation distribution inside the reactor bed coupled with higher overall productivity. Easy catalyst regeneration One more feature is the capability of controlling the hydrocarbon product High distribution. mass transfer rates High heat transfer rate Wide product spectrum Advantage 16 Disadvantage
Supercritical Phase Reaction Supercritical Phase Introduction of supercritical hydrocarbon solvent Syngas Solvent Propane Pentane Hexane Active site Fixed Bed Reactor SC Liquid-like density and heat capacity Gas-like diffusivity and transport properties P L V Elbashir, Bukur, Durham, Roberts. 2010 AIChE J. 56 (3) 997. 17 T
Region 1: Exothermic reaction occurring in single phase focus on hot spot prevention Region 2: Wax formation tailor pore structure to facilitate wax extraction from catalyst Region 3: Trickle bed regime tailor pore structure and surface wettability to maximize secondary reactions 18
Weight Fraction 0.6 0.5 Comparison SCF-FTS & Gas Phase FTS Product Distribution & Conversion CO Conv. = 65% CO Conv. = 73% T= 240 C, P syngas =20 bar, 15% Co/ Al 2 O 3 P tot = 65 bar 0.4 0.3 Gas-Phase Sc-Hexane 0.2 0.1 0 Light Hydr. Gasoline Diesel Heavy Hydr. & Wax Huang, Elbashir, Roberts 2005. Industrial & Engineering Chemistry Research 43, 6369. 19
Why is the selective control of Fischer Tropsch products important? Start with the control of the polymerization nature of FTS reactions Improve product yields and purity Simplify separation processes Minimize production cost
What it takes to design a novel reactor technology? Elbashir, Eljack. 2010 in Advances in Gas Processing: Elsevier, vol. 2; 369. 21
The Design Phases of Novel Reactor Advisory Board Process Design: Energy Integration & Optimization Phase Behavior & Thermodynamics Process Control Products Processing Kinetics & Product Distribution Reactor Design & Experimental Campaign In situ Reactor Behavior Elbashir, Eljack. 2010 in Advances in Gas Processing: Elsevier, vol. 2; 369. 22
Microscale Studies: Simulation & Experimental Phase Behavior Hot Spots Kinetics, Chain growth Diffusion Limitations Bao, El-Halwagi, Elbashir 2010. Fuel Processing Technology 91(7) 703-713. 23
Macroscale Studies P&ID Energy Optimization Process Control Solvent Recovery Solvent Selection Reactor Configuration Synthetic Fuels Formulation & Characterization 24
Catalyst Bed Behavior in SCF-FTS Mogalicherla, Elmalik& Elbashir (2012) Chem. Eng. Prog.: Proc. Intes. 62, 59-68. 25
NMR Relaxometry Gladden, et al. 2009. J Phys. Chem. C 113, 6610. Liquid & gas velocity profile 3D visualization Gladden et al. 2009. JMR 196, 142. 26
Simulation Examining the most applicable solvent for commercial SCF-FTS based on phase behavior studies & cost Experimental Solvent Price ($ per tonne)* n-pentane 989-1055 n-hexane 955-985 Light Naphtha 720-775 Naphtha 690-761 Solvent Naphtha 875-885 Gasoline 722-745 * Selected solvent prices, as provided from the ICIS price reports. Elmalik, Tora, El-Halwagi, Elbashir 2011 Fuel Proc. Techn., 92; 1525. 27
SSI Examining the Most Applicable Solvent for Commercial SCF-FTS Based on Safety & Economic Assessment Cost SSI Total =SSI 1 + SSI 2 + SSI 3 + SSI 4 300 n-pentane 250 200 n-hexane n-heptane n-octane n-nonane 150 n-decane Blend 1 100 Blend 2 Solvent Price ($ per tonne)* n-pentane 989-1055 n-hexane 955-985 Light Naphtha 720-775 Naphtha 690-761 Solvent Naphtha 875-885 Gasoline 722-745 Elmalik, Tora, El-Halwagi, Elbashir (2011) Fuel Proc. Techn., 92; 1525. 28 50 0 0 2 4 6 8 10 Cost ($/gallon) Hamad, El-Halwagi, Elbashir, Manann (2012) J. Loss Prevention in the Process Industries, online. Blend 3 Blend 4 Blend 5
Design of Optimized Sequence for Solvent Separation & Recycle mixer FT reactor recycle Fresh feed (syngas, solvent) FT products Flash column 1 Flash column 2 Flash column 3 Radfrac Distillation 1 Radfrac Distillation 2 Heavy products Permenant Gas 1 Flash column 4 Radfrac Distillation 3 Permenant Gas 2 Solvent 2 Condenser Solvent 1 Replace RadFrac column with flash column Water mixer FT reactor recycle Fresh feed (syngas, solvent) FT products Flash column 1 Flash column 2 Flash column 3 Radfrac Distillation 1 Radfrac Distillation 2 Heavy products Permenant Gas 1 Condenser Flash column 4 Radfrac Distillation 3 Permenant Gas 2 Solvent 2 Condenser Solvent 1 Add a condenser after the flash column Water Lowest Energy and Higher Efficiency 29
Design of Optimized Sequence for Solvent Separation & Recycle Fresh feed mixer (syngas, Permenant solvent) Permenant Gas 2 Flash Gas 1 Solvent 2 FT reactor Condenser column 1 Flash FT column 4 products Flash Water column 2 Radfrac Distillation 2 Radfrac Flash Distillation 3 column 3 Solvent 1 Radfrac Distillation 1 Heavy products recycle Replace RadFrac column with flash column Separation design constraints Process Alternatives Operating variables mixer Fresh feed (syngas, solvent) Flash FT reactor column 1 FT products recycle Oil-Solvent input Flash column 2 Flash column 3 Radfrac Distillation 1 Radfrac Distillation 2 Heavy products Permenant Gas 1 Condenser Flash column 4 Radfrac Distillation 3 Permenant Gas 2 Solvent 1 Condenser Water Solvent 2 Add a condenser after the flash column mixer syngas mixer Pressure and temperature control for supercritical condition FT reactor Pump Fresh solvent FT products Flash column 1 recycle no Objective Flash column 2 yes Flash column 3 Radfrac Distillation 1 Process Simulation Process Integration Radfrac Distillation 2 Experimental Verification & Cost analysis Heavy products Design, Operating output Optimize the process Permenant Gas 1 Flash column 4 Radfrac Distillation 3 Solvent 1 Permenant Gas 2 Condenser Water Solvent 2 30 Buping, Elbashir, El-Halwagi, Elbashir (2012) ISSF, P0605; 1-8.
Future generation of FTS Reactor Bed N 2 @0.05m/s N 2 @0.05m/s N 2 @0.2m/s Packed Bed @ 207 particles (60 vol.%) N 2 @0.2m/s MFEC@ 207 mm Particle and 3.6 vol% 12 mm Copper fibers 31
Cleaner skies Qatar Airways makes historic journey with first GTL fueled commercial flight from London Gatwick to Doha New Gas-to-Liquids fuel offers diversity of supply and better local air quality at busy airports 32
Consortium A unique collaboration between industry and academia partners. Each partner works on specific topics and collaborate towards the overall objective. Funding Agencies Technical Guidance The testing is split up as follows: Properties Testing Combustion Testing Performance Review 33
Hydrocarbon Groups Species & Carbon Number distribution in a conventional jet fuel (Jet A-1) versus a synthetic GTL kerosene (SPK). *GCxGC data provided by Shell 34
Hydrocarbon Groups Group Structure normal-paraffins iso-paraffins Naphthenes (cyclo-paraffins) mono-aromatics di-aromatics Naphthenic-mono- Aromatics 35
Research Goals Our role is to develop experimental, statistical and visualization techniques capable of correlating fuel s hydrocarbon structure with their properties. Working with industry & academia partners to develop future synthetic jet fuels obtained via Gasto-Liquid [GTL] (i.e. Synthetic Paraffinic Kerosene [SPK]). 36
Overview of TAMUQ Fuel Characterization Lab State-of-the-art experimental facilities 37
Area of crucial focus cyclo-paraffin ASTM specification D1655 Property Min Max Density (g/ml) 0.775 0.84 Region of optimal properties Property Min Max Flash Point ( C) 42 Property Min Max Freezing Point ( C) -47 GTL Kerosene n-paraffin Raza, Elmalik & Elbashir 2011. Perp. Fuel Chem. Div. 56; p. 431. 38 iso-paraffin
Properties role on fuels performance Courtesy of Dr. John Moran from Rolls Royce 39
Detailed Composition & Products Analysis
Density Optimized synthetic jet fuel composition Heat Content Flash Point Freezing Point Rhman, et al. 2012. ENERGY & FUELS. ACS Meeting. San Diego, CA. 41
Optimized synthetic jet Fuel composition Freezing Point Rhman, et al. 2012. ENERGY & FUELS. ACS Meeting. San Diego, CA. 42
Freezing Point Explaining trend of composition vs. properties 43
Freezing Point - Images IB6 = -51.6 IB21 = -33.7 IB10 = -46.1 SPK = -56.5 Raza, Elmalik & Elbashir 2011. Perp. Fuel Chem. Div. 56; p. 431.
Further Step Purpose of the next phase is to enhance our understanding of how the properties vary with jet fuel hydrocarbon composition. Objectives Role of aromatics on enhancing certain properties (Density, Elastomer compatibility) and improving elastomer swelling behavior Role of hydrocarbon number in determining the behavior of jet fuel Role of other hydrocarbons, which can mimic the role of aromatics on certain properties (i.e.: Density) 45
Skeleton of 3-D Pyramid 46
Artificial Neural Network 3-D Visualization 47
Summary The first phase of the micro & macro scale design successfully completed and resulted in an advanced SCF-FTS lab scale reactor. Designed technology capable of maximizing the production of ultraclean fuels and value-added chemicals. Established global collaborations with both industry and academia. Conducting major research campaign in advancement of synthetic jet fuels properties and formulation of new generations. 48
Research Team Dr. Bao Buping; Mohamed Noureldin 49
Students Participations & Awards Poster American Chemical Society Meeting in San Diego. Mar 2012 Recognition from the Energy & Fuels Division of the American Chemical Society First Place Poster in the 3rd International Gas Processing Symposium. March 2012 Research Team Award from the Chemical Engineering Program Texas A&M University: April 2012
Major Awards Qatar Foundation Best Energy & Environment Research Programme of the Year. October 2012 Texas A&M University & Qatar Foundation Best Visualization Development Project in the 2012 Competition. May 2012
Student Researchers Haider Ramadhan Dhabia Al-Mohandi Maryam Manjohari Jahanur Rahman Asma Saida Maria Orillano Maha Kafood Moiz Bohra Natalie Hamad Mariam Al-Meer
Research Associates Samah Warrag Elfatih Elmalik Dr. Suresh Reddy Salima Mamikova Ibrahim Al-Naimi Dr. Jan Blank Syed Hussani Laial Bani Nasser Dr. Rehan Houssein Bilal Raza Dr. Aswani Mogalicherla
Acknowledgements Collaborators Prof. Mahmoud El-Halwagi Prof. Juergen Hahn Prof. Benjamin Whilhite Prof. Lynn Gladden Prof. Christopher Roberts Prof. Dragomir Bukur Prof. Marcelo Castier Prof. Fadwa Eljac Dr. John Moran Paul Bogers Willem Scholten Dr. Joanna Bauldreay Prof. Chris Wilson Prof. Manfred Aigner Dr. Patrick declerqe Prof. Rafiqul Gani Industry Advisory Board Willem Scholten Dr. Jim Rigby Dr. Ernest De Toit (former) Rashid Al-Rashdi Funding Agencies: 54
Acknowledgements This publication was made possible by following Grants from the Qatar National Research Fund (a member of Qatar Foundation). The statements made herein are solely the responsibility of the authors. Funding : 55
Thank you CHEMICAL ENGINEERING PROGRAM 336F Texas A&M Engineering Building Education City PO Box 23874 Doha, Qatar Tel. +974.423.0017 Fax +974.423.0065 chen@qatar.tamu.edu http://chen.qatar.tamu.edu 56
Backup Slides 57
Selectivity % 40 35 30 25 20 15 10 5 Comparison SCF-FTS & Gas Phase FTS Selectivity vs. Conversion CH4 Selectivity CO2 Selectivity 0 45 55 65 75 Syngas conversion% Elbashir, Dutta, Seehra, Roberts 2005. Applied Catalysis A: General 285, 169. Gas-phase FTS, 230-250 C, P = 15-20 bar 15% Co/SiO 2 (HSA), Syngas FR = 50-100 sccm/g
Selectivity % Comparison SCF-FTS & Gas Phase FTS Selectivity vs. Conversion 20 15 CH4 Selectivity % CO2 Selectivity % 10 5 0 45 50 55 60 65 70 75 80 Syngas Conversion % Elbashir, Dutta, Seehra, Roberts 2005. Applied Catalysis A: General 285, 169. Sc-Hexanes FTS, 230-250 C, P = 45-65 bar 15% Co/SiO 2 (HSA), Hexanes/syngas (molar) = 3 Syngas FR 59 = 50-100 sccm/g cat
Activity & Selectivity Co 3 O 4, Co +2 -Al 2 O 3 100 80 60 Stability of the same Catalyst in Gas-Phase FTS 230 C 250 C Co 3 O 4 fcc Co 0 Syngas Conversion % CH4 Selectivity % Series3 230 C 40 20 0 0 50 100 150 Time-on-stream (hr) Elbashir, Dutta, Seehra, Roberts 2005. Applied Catalysis A: General 285, 169. 60
Activity & Selectivity Co 3 O 4, Co +2 -Al 2 O 3 100 80 60 Stability of the same Catalyst in Supercritical Phase FTS 240 C 230 C 250 C Syngas Conversion % CH4 Selectivity % Series3 240 C hcp Co 0 40 20 0 0 50 100 150 200 250 Time-on-stream (hr) Elbashir, Dutta, Seehra, Roberts 2005. Applied Catalysis A: General 285, 169. 61
ln(wn/n) Opportunity for Selective Control of Hydrocarbon Product Distribution -1 SC -3-5 α = 0.83 P L V -7 P=65 bar T -9-11 250-13 0 4 8 12 16 20 24 Carbon number Elbashir, Roberts 2005. Industrial & Engineering Chemistry Research 44, 505.
Experimental and predicted rate of methane formation in high pressure gas-phase FTS rch4 formation (mmol/gcat.min) 0.6 0.5 0.4 0.3 0.2 0.1 0 0 0.5 1 1.5 2 2.5 gas-phase actual-rate gas-phase predicted rate H 2 /CO feed ratio T = 240 C, P T = 60 bar P syngas = 15 bar, P helium = 45 bar, Helium/syngas (molar ratio) = 3
rch4 formation (mmol/(gcat.min) Experimental and predicted rate of methane formation in SCH-FTS 0.6 0.5 0.4 0.3 0.2 0.1 SCH-actual rate SCH predicted-rate 0 0 0.5 1 1.5 2 2.5 H 2 /CO feed ratio T = 240 C, P T = 60 bar P syngas = 15 bar, P hexane = 45 bar, Hexane/syngas (molar ratio) = 3
Enhanced α-olefin incorporation in the chain growth process Dynamic adsorption/desorption equilibrium 1 Heat of adsorption 2 Pressure & residence time 3 Reaction media and phases 4 Feed ratio, catalyst type, temp., etc.
(4) Kinetics of the SCF-FTS Modified Reaction Pathway and Chain Growth Model for SCF-FTS R n+1 +S R n+3 +S * R n.s H.S CH 3.S R n.h+s R n+2.s * H.S* CH 3.S R n+2.h+s * CH 3.S CH 3 R n-2 -CH+S CH 3.S * CH 3 R n -CH+S * R 1 C.S * +H.S * CH.S * +S * Regular chain growth model on S Enhanced olefin incorporation on S*
ln(wn/n) C 1 * Enhanced incorporation of α-olefins in SCH Phase C 3 H 8 C 2 H 4 + C 1 * C 2 * + C 1 * C 3 H 8 C 4 H 10 C 5 H 12 C n H 2n+2 C 3 H C 6 n+1 H 2n+4 C n+m H 2(n+m)+2 C 4 H 8 C 5 H 10 C n H 2n C n+1 H 2(n+1) C n+m H 2(n+m) + C C 3 * 1 * + C C 4 * 1 * C 5 * + C 1 * C n * + C 1 * Cn+1 * + C 1 * Cn+m * -1-3 -5-7 -9 0 5 10 15 20 25 Carbon Number
Energy Integration & Overall Techno-economic Assessment
Techno-economic Assessment of the Optimized Sequence
Comparison between the three reactors
with condenser with no con replace radfrac flash sequence heavy column Category Item unit unit Pricesnote Amount/yr total MM$/yr Chemicals 4760BTU/LB syngas $/GJ 13 59,847,124 778.01 56,220,266 731 56,220,266 731 56,220,265 731 56,220,266 731 Catalyst fixed bed 4 1 1-1 1 1 hexane $/gal 1.15 89,790,385,440 103,258.94 89,790,385,440 103,258.94 89,790,385,440 103,259 89,790,385,440 103,259 89,790,385,440 103,259 - - - - - - - - - - - - - - - - annual operating O&M labo %FCI/yr 4 54 54-56 52 52 operating labor 131 131-131 131 131 supervisio%labor 90 118 118-118 118 118 capital cha%fci/yr 15 203 202-210 196 194 Energy utility 1,715 1,715-1,880 1,530 1,592 after heat integration 1,064 1,064-1,110 1,047 945 - - - - - - - - - - - - Porducts sale sale 3,619 sale 3,619 sale 3,619 sale 3,621 sale 3,611 diesel $/bbl 82 43,800,000 3,592 43,800,000 3,592 43,800,000 3,592 43,827,060 3,594 43,709,310 3,584 gasoline $/bbl 63 - - - - - - H2 $/kg 2 - - - - - - - - - - H2O $/1000gal 1.2 1,044,119 1 1,026,183 1 1,026,183 1 1,026,183 1 1,044,119 1 tailgas $/bbl 50 517,570 26 525,562 26 525,562 26 525,563 26 517,570 26 hexane $/gal 1.15 89,774,303,982 103,240 89,699,200,892 103,154 89,699,200,892 103,154 89,698,503,869 103,153 89,774,303,982 103,240 - - Total operating cost 3,017 3,056-3,231 2,863 2,836 - - annual after cash profit 466 437-307 583 596 ROI 0.29 0.28-0.19 0.38 0.39 after heat integration operating cost 2,366 2,405 2,461 2,381 2,189 annual after cash p 954.68 925.71 884.56 945.18 1,080.92 ROI 0.60 0.58 0.54 0.62 0.71
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