Departamento de Engenharia Química Rua Dr. Roberto Frias, S/N 4200-465 Porto Portugal http://lsre.fe.up.pt lsre@fe.up.pt Four separations to change the world A. Ferreira A. M. Ribeiro, A. E. Rodrigues
Team Cyclic Adsorption Processes Alírio E. Rodrigues Emeritus Professor José Miguel Loureiro Associated Professor Alexandre F. P. Ferreira Researcher Post-Doc Fellows Ana Mafalda Ribeiro Researcher Mariana M. Moreira Rui Faria Jonathan Silva Nuno Graça Filipe Cunha Dania Constantino Ph.D. Students Qian Shi Pedro Gomes Vanessa Martins Maria J. Regufe Idelfonso Nogueira Marcia Silva 2
Former members (with contributions for the 4 separations) Francisco Avelino da Silva (Currently at Universidade de Aveiro) José Silva (Currently at I. P. de Bragança) Carlos Grande (Currently at Sintef, Norway) Miguel Ângelo Granato (Currently at UFSC, Brazil) Nabil Lamia (Currently at TOTAL, Belgium) Miguel Jorge (Currently at University of Strathclyde, UK) Pedro Sá Gomes (Currently at BASF, Germany) João Carlos Santos (Currently at Jacobs Engineering, Belgium) Marta G. Plaza (Currently at INCAR-CSIC, Spain) Guler Narin (Currently at Usak University, Turkey) Mazaki Okada (Currently at Nihon University, Japan) Marta Campo (Currently at Jacobs Engineering, Belgium) Patrick Barcia (Currently at SysAdvance) Patricia Mendes Rui Ribeiro (Currently at Universidade Nova de Lisboa) Filipe V. Lopes Simone Cavenati (Currently at Universidade do Vale do Itajaí, Brazil) Miriana Minceva (Currently at T. U. Munchen, Germany) Viviana Silva (Currently at BASF, Germany) Marta Silva (Currently at GALP) 3
Motivation David S. Sholl & Ryan P. Lively 26 April 2016 Corrected: 11 May 2016 4
Motivation Seven chemical separations to change the world Hydrocarbons from crude oil. Uranium from seawater Alkenes from alkanes Greenhouse gases from dilute emissions Rare-earth metals from ores Benzene derivatives from each other Trace contaminants from water 5
Motivation - Seven chemical separations to change the world Next steps (by the authors) Researchers and engineers must consider realistic chemical mixtures. Most academic studies focus on single chemicals and infer the behaviour of mixtures using this information. The economics and sustainability of any separation technology need to be evaluated in the context of a whole chemical process. Serious consideration must be given early in technology development to the scale at which deployment is required. Physical infrastructure such as academic and industrially operated test beds will be needed to take new technologies from the lab to pilot scales so that any perceived risk can be reduced. Managing this will require academia, government agencies and industry partners to collaborate. Fourth, current training of chemical engineers and chemists in separations often places heavy emphasis on distillation. Exposure to other operations such as adsorption, crystallization and membranes is crucial to develop a work force that is able to implement the full spectrum of separations technologies that the future will require. 6
Separations of Alkenes from Alkanes Manufacturing plastics such as polyethene and polypropene requires alkenes hydrocarbons such as ethene and propene, also known as olefins. Global annual production of ethene and propene exceeds 200 million tonnes, about 30 kilograms for each person on the planet. The industrial separation of ethene from ethane typically relies on high-pressure cryogenic distillation at temperatures as low as 160 C. Purification of propene and ethene alone accounts for 0.3% of global energy use, roughly equivalent to Singapore's annual energy consumption. 1) Adhesives Carpeting Cosmetics Fertilizers Paints Rubers Fabrics Plastics 1) Nature 532, 435 437, 2016 7
Ethylene Production Polyethylene and polypropylene are produced by the polimerization of ethylene and propylene (purity grade 99.9%), in homopolymer or copolymer form (C2 & C3 splitters) 8
Distillation vs Adsorption 78 m Vs. C2 splitter Gas phase SMB PSA With 2 downstream separations 9
Binderless 13X Beads Adsorbent: Binderless 13X zeolite beads (provided by partners at CWK) 1) Property Shape Particle diameter Value Beads 1.2 2.0 mm Apparent density (r p ) * 1072 kg m -3 Crystal radius (r c ) 2.0 10-3 mm 1) J. Jänchen, K. Schumann, E. Thrun, A. Brandt, B. Unger, U. Hellwig, Int. J. of Low-Carbon Technologies, 7 (2012) 275-279. 10
Equilibrium Isotherms and Heats of Adsorption -DH, kj/mol 45 40 C 3 H 8 35 30 25 C 2 H 4 C 2 H 6 0.0 1.0 2.0 3.0 q, mol/kg Component q A,sat (mol kg -1 ) q B,sat (mol kg -1 ) q sat (mol kg -1 ) b A, (bar -1 ) b B, (bar -1 ) -DH A (kj mol -1 ) -DH B (kj mol -1 ) Ethane 3.93 0 3.93 1.02 x 10-4 0 26.50 0 Ethylene 2.91 1.58 4.49 3.14 x 10-5 1.71 x 10-5 37.00 30.11 Propane 2.79 0.69 3.48 7.77 x 10-5 1.33 x 10-6 35.32 38.00 Propylene 2.71 1.14 3.85 1.52 x 10-4 1.25 x 10-7 39.82 50.20 11
yi SMB Experiments 4 Zones Paraffin/ Olefin 0.48C 2 H 6 / 0.52C 2 H 4 13X Binderless Adsorbent Configuration ts, s T, K P, kpa Open: 4-2-1-1 110 373 130-220 1.0 Internal Profile 50% 0.8 0.6 0.4 0.2 0.0 0 1 2 3 4 5 6 7 8 Columns Internal profile at half time step as function of column number (25 th cycle). 12
yi yi 48% Ethane + 52% Ethylene 0.50 Raffinate 0.50 Extract 0.40 0.40 0.30 0.30 0.20 0.20 0.10 0.10 0.00 0 22 44 66 88 110 Time Step, s 0.00 0 22 44 66 88 110 Time Step, s 13
Performance Parameters C 2 H 4 C 2 H 6 Run Pu X, % Rec X, % DC* Pro X ** Pu R, % Rec R, % DC* Pro R ** 1 99.94 98.99 1.12 85.12 96.12 99.78 2.19 23.03 2 99.89 99.46 1.14 57.08 99.40 99.88 2.00 55.14 3 99.95 99.50 0.97 81.34 98.28 99.84 2.91 25.09 4 99.85 99.65 0.99 52.39 99.60 99.83 2.83 49.37 5 99.93 99.57 0.90 85.78 98.09 99.69 2.71 20.42 6 99.78 99.82 0.92 59.71 99.77 99.72 2.63 49.00 * m 3 STP,iC4H10/kg C3 * * kg C3 h -1 m ads -3 14
Greenhouse gases from dilute emissions Anthropogenic emissions of CO 2 and other hydrocarbons, such as methane released from refineries and wells, are key contributors to global climate change. It is expensive and technically difficult to capture these gases from dilute sources such as power plants, refinery exhausts and air. Liquids such as monoethanolamine react readily with CO2, but because heat must be applied to remove CO 2 from the resulting liquid, the process is not economically viable for power plants. If the approach was applied to every power station in the United States, CO 2 capture could cost 30% of the country's growth in gross domestic product each year. Cheaper methods for capturing CO 2 and hydrocarbon emissions with minimal energy costs need to be developed. 1) Gas Biogas 1 Landfill gas 1 1) Nature 532, 435 437, 2016 Natural gas 1 Slurry feed Syngas 2 Dry feed syngas 2 H 2 lean syngas 2 H 2 -rich syngas 2 CH 4 (%) 90-70 65 90 - - - - Other Hydrocarbons (%) - - 9 - - - - H 2 (%) - 0-3 - 35 28 1 95 CO 2 (%) 30-40 15-50 1 14 3 21 1 CO (%) - - 0.3 50 64 76 1 N 2 (%) ~ 0.2 5-40 - 1 2 2 3 O 2 (%) - 0-5 - - - - - 15
CO 2 capture Natural gas / Biogas Industrial processes Post-combustion Pre-combustion
CO 2 capture Processes Materials Pressure Swing Adsorption (PSA) Temperature Swing Adsorption (TSA) Electric Swing Adsorption (ESA) Pellets: Carbons, Zeolites, Monoliths: Carbons, zeolites, composite materials
Binderless 5A Zeolite LTA Ca +2 form KÖSTROLITH 5A BFK Beads, 1-2 mm 18
Equilibrium Isotherms 19
PSA Experiments STEP Pressurization Coc. Adsorption Depressurization Coc. Blowdown Purge N 2 N 2 N 2 N 2, CO 2 N 2, CO 2 CO 2 CO 2 Pressure (bar) 0.35 4 4 4 1.1 1.1 0.16 0.35 Duration (s) 1152 104 204 198 Feed (SLPM) 0.38 - - 0.2 Feed composition (%) 80 N 2 20 CO2 - - 100 N2 20
T (K) P (bar) F (mol/s) F (mol/s) PSA Experiments 1.0 N2 0.8 CO2 0.6 0.4 0.2 0.0 0 1000 2000 3000 4000 5000 6000 t (s) 360 TT 24.2 cm 350 TT 13.2 cm 340 TT 2.3 cm 330 320 310 300 290 0 1658 3316 4974 6632 8290 9948 11606 13264 14922 16580 t (s) 1.0 N2 0.8 CO2 (n+1) th cycle 0.6 0.4 0.2 0.0 0 500 t (s) 1000 1500 n x t cycle (n +1) x t cycle 5.0 4.0 3.0 2.0 1.0 0.0 0 2000 4000 6000 t (s) 21
Benzene derivatives from each other The supply chains of many polymers, plastics, fibres, solvents and fuel additives depend on benzene, a cyclic hydrocarbon, as well as on its derivatives such as toluene, ethylbenzene and the xylene isomers. These molecules are separated in distillation columns, with combined global energy costs of about 50 GW, enough to power roughly 40 million homes. 1) 1) Nature 532, 435 437, 2016 22
Benzene derivatives chalenge Properties of the different components Compound Abbreviation d (Å) [a] T boil (K) T fus (K) Sieving o-xylene o-x 7.4 417.4 248. 0 Intensive Distillation Low recoveries m-xylene m-x 7.1 412.1 225.0 p-xylene p-x 6.7 411.4 286.4 ethylbenzene eb 6.7 409.2 179.0 No Sieving Specific interactions [a] Loiseau T, Serre C, Huguenard C, Fink G, Taulelle F, Henry M, Bataille T, Férey G. A Rationale for the Large Breathing of the Porous Aluminium Terephthalate (MIL-53) Upon Hidration. Chemistry - A European Journal. 2004;10:1373-1382. 23
New adsorbents A reverse shape selective MOF: UiO-66(Zr) UiO-66(Zr) 6 Å Tetrahedral Cage MIL-125(Ti)_NH 2 11 Å Octahedral Cage Para-xylene selective MOFs: MIL-125(Ti) & MIL-125(Ti)_NH 2 Effect of Ethylbenzene (eb) and NH 2 group in the p-x/m-x selectivity 1.6 MIL -125(Ti) -NH 3.0 2 effect MIL -125(Ti)_NH 2 Ternary Mixture Ternary Mixture 1.4 Quaternary Mixture 2.5 Quaternary Mixture a p-x/m-x 1.2 1.0 a p-x/m-x 2.0 1.5 + eb 0.8 1.0 Octahedral (12.5 Å) Tetrahedral (6 Å) 0.6 0 1 2 3 C p-x, mol dm -3 0.5 0 1 2 3 C p-x, mol dm -3 24
Process optimization & Process Integration Parex optimization and hybrid adsorption/reaction processes for xylenes production/separation Adsorption Modeling Simulation Optimization Parex Isomar Isomerization Gas Phase Liquid Phase 25
Hydrocarbons from crude oil The main ingredients for manufacturing fossil fuels, plastics and polymers are hydrocarbons. Each day, refineries around the world process around 90 million barrels of crude oil roughly 2 litres for every person on the planet. Most do so using atmospheric distillation, which consumes about 230 gigawatts (GW) globally, equivalent to the total energy consumption of the United Kingdom in 2014 or about half that of Texas. It is feasible in principle to separate hydrocarbons according to their molecular properties, such as chemical affinity or molecular size. Membrane-based separation methods, or other non-thermal ones, can be an order of magnitude more energy efficient than heat-driven separations that use distillation. But little research has been done. 1) 1) Nature 532, 435 437, 2016 26
Propane adsorbed (mol kg -1 ) Propylene adsorbed (mol kg -1 ) Amount adsorbed (mol kg -1 ) C3/C4 Separation Samples: MIL-100(Fe) granulates (KRICT) 2.542 mm 8 7 6 5 4 3 2 1 0 Propane Propylene Isobutane 323 K 373 K 423 K Langmuir 0 100 200 300 400 500 Pressure (kpa) Activation at 423 K 8 7 6 5 4 3 2 1 0 323 K 373 K 423 K Langmuir 0 100 200 300 400 500 Pressure (kpa) Activation at 423 K 5 mm 8 7 6 5 4 3 2 1 0 Activation at 423 K 323 K 373 K 423 K Langmuir 0 100 200 300 400 500 Pressure (kpa) 27
Molar flowrate (mmol s -1 ) Molar flowrate (mmol s -1 ) C3/C4 Separation 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 Propane (exp) Isobutane (exp) Propane (sim) Isobutane (sim) 0 500 1000 1500 2000 2500 3000 Time (s) 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 Propylene Isobutane Propylene (sim) Isobutane (sim) 0 500 1000 1500 2000 2500 3000 Time (s) 28
C6 Isomers Separation - Adsorbents Zeolites: MFI MOFs: ZIF-8 29
C6 Isomers Separation Process Enhancement Octane Upgrading of TIP Processes by Recycling in a Layered PSA with 5A Zeolite /BETA zeolite. Product average RON as a function of the zeolite 5A/BETA layer ratio (L 5A /L B ) and purge-to-feed (P/F) ratio at T = 523 K and t press /t feed = 20/80 s. 30
Acknowledgments 31