CBE301. Chemical and Biomolecular Engineering Laboratory (2015 spring) Experiment 1 n-Butane / iso-Butane Adsorptions with Molecular Sieve 5A (CaA Zeolite) Zeolites : Microporous Crystalline Aluminosilicates Natural Zeolites Synthetic Zeolites Zeolite (= “boiling stone”) : produces steams under heating. Natural zeolite is generated by hot spring & volcano activities. Over 150 zeolite structural types have been identified (about 40 natural zeolite) Compositions and Structures Mn+2/nO Extra-framework cation • [Al2O3 • xSiO2] Framework • yH2O Adsorbed phase Overall charge of TO4 (T: Si or Al) SiO4 : neutral [(+4) + 4×(-1)] AlO4 : -1 [(+3) + 4×(-1)] Crystalline microporous aluminosilicate minerals → high surface area (100 – 800 m2/g) Three-dimensional network of AlO4 and SiO4 tetrahedra linked by sharing all of the oxygens For charge-balancing, extra-framework cation Mn+ is required nearby the aluminum sites within the zeolite micropores Si-O-Si, Si-O-Al bonds are thermodynamically allowed, but not Al-O-Al bond 1 ≤ Si/Al ≤ ∞ : depending on the structural type Framework Structures: 3-Letter Codes http://izasc.ethz.ch/fmi/xsl/IZA-SC/ft.xsl SOD structure Sodalite (Si/Al=1) LTA structure NaA (Si/Al=1) FAU structure NaX (Si/Al=1.2) NaY (Si/Al=2.5) MFI structure ZSM-5 (Si/Al>10) Silicalite (Si/Al=∞) Typical Synthesis of Zeolite : Hydrothermal Crystallization 1. Amorphous inorganic precursors containing silica and alumina are mixed together with a cation source (generally Na+), usually in a highly basic (high pH) medium. 2. The initial synthesis gel is heated in the temperature range of 80 – 200 °C within a sealed autoclave for hydrothermal crystallization. 3. For some time after raising to synthesis temperature, the reactants remain amorphous. 4. After the above “induction period”, crystalline zeolite product can be detected. Example of Zeolite Synthesis : NaA Zeolite (LTA Structure) ▶ Batch composition: 3.165Na2O : Al2O3 : 1.926SiO2 : 128H2O Zeolite synthesis compositions are often indicated in an ‘oxide formula’ ▶ Procedure (for 10 g dry product) (1) [80 mL water + 0.723 g sodium hydroxide], mix gently until NaOH is completely dissolved. Divide into two equal volumes in polypropylene bottles. (2) [One-half of (1) + 8.258 g sodium aluminate], mix gently in capped bottle until clear. (3) [Second half of (1) + 15.48 g sodium metasilicate], mix gently in capped bottle until clear. (4) [(2) + (3)], pour silicate solution into aluminate solution quickly; a thick gel should form. Cap tightly and mix until homogenized. ▶ Crystallization Vessel: 100-150 mL polypropylene bottle (sealed) Temperature: 100 ℃ Time: 3-4 hours Agitation: stirred or unstirred Important Properties of Zeolites : Cation-Exchange Mn+2/nO Extra-framework cation • [Al2O3 • xSiO2] Framework • yH2O Adsorbed phase Water Softner (Detergent Builder) Na+ Na+ Na+ Ca2+ Na+ Ca2+ Na+ Na+ Important Properties of Zeolites : Thermal Stability Generally speaking, zeolites are thermally stable even at very high temperatures. The degradation temperature of low-silica zeolite (Si/Al<3) is around 700 ℃, while highly siliceous zeolites are stable even up to 1000 ℃. The presence of steam dramatically facilitates the structural collapse of zeolites at the same temperature. Thermal stabilities of highly aluminous zeolites are greatly affected by the types of extraframework cations. Important Properties of Zeolites : Chemical Stability All zeolites are very stable in organic solvents and in neutral water High-silica zeolites are unstable at strongly basic condition (silicon is leached out) Low-silica zeolites are unstable in acidic condition (aluminum is leached out) In general, high-silica zeolites are thermochemically more stable than low-silica zeolite. Sieve (체) Important Properties of Zeolites : Molecular Sieving Effect Pore aperture size KA : ~3 A NaA : ~4 A CaA : ~4.5 A Figure. Correlation between effective pore size of various zeolites in equilibrium adsorption over temperature 77 to 420 K, with the kinetic diameters of various molecules as determined from the Lennard-Jones potential relation. (from Breck, 1974) Example of Molecular Sieving 5A zeolite (CaA zeolite, pore aperture size: 4.5 A) is commercially used in large-scale to separate n-butane/iso-butane Due to the molecular sieving effect, only a smaller n-butane can diffuse to the pore of CaA, but a larger iso-butane cannot. 4A n-butane (kinetic diameter : 4.3 A) 5A iso-butane (kinetic diameter : 5.0 A) Using such size-selective adsorption properties of zeolites, pressure swing adsorption (PSA) process can be designed for the separation of mixed gases. Pressure Swing Adsorption (PSA) PSA : Continuous cyclic separation process for gas mixture under the pressure change (swing) with difference of affinity between certain molecules and adsorbents (e.g., zeolites, activated carbon, molecular sieves, etc.). Application : Air separation, H2 purification from steam reforming, hydrocarbon separation, natural gas upgrading, and flue/exhaust gas purification Adsorption Isotherm Measurement Vm: manifold volume (calibrated) Vcell: cell volume except the volume of sample Vtot: Vm+Vcell <Helium determination of Vtot and Vcell> Since He does not adsorb at all, it can be used for determining the cell volume except the volume of sample. PVm = P`Vtot r = Vtot/Vm = P/P` <Adsorbed amount> ni: ‘increment’ of adsorption capacity during i th dosing n1 = P1Vm/RT1 - P1`Vtot/RT1` = Vm/R * (P1/T1 - rP1`/T1`) n2 = (P2Vm/RT2 + P1`Vcell/RT1`) - P2`Vtot/RT2` Dosing amount through manifold during 2nd dosing Remained gas amount in the cell during previous dosing = (P2Vm/RT2 + P1`(r-1)Vm/RT1`) - rP2`Vm/RT2` = Vm/R * (P2/T2 + P1`(r-1)/T1` - rP2`/T2`) ni = Vm/R * (Pi/Ti + Pi-1`(r-1)/Ti-1` - rPi`/Ti`) Ni (total adsorbed amount until i th dosing) = n1 + n2 + ··· + ni Example of Gas Adsorption-Desorption Isotherm Experiment Temperature controller Adsorption measurement instrument Pressure indicator Pressure sensor Helium Vacuum n-Butane iso-Butane Cell Heating mantle Experiment 1. Degassing 5A (CaA) Zeolite Beads 1) Weight an empty cell. 2) Put approximately 1 g of 5A zeolite beads into the cell. 3) Weigh (sample+cell). 4) Connect the cell to the adsorption measurement instrument. 5) Cover the cell with a heating mantle and increased the temperature to 673 K under vacuum. Maintain the temperature at 673 K for 4 h. 6) After 4 h, remove the heating mantle and cool down. Backfill the cell with helium gas up to about 1 atm. 7) Weigh (degassed sample+cell). 8) Calculate the weight of degassed sample. 9) Connect the cell again to the adsorption measurement instrument and evacuate again. Experiment 1. Degassing 5A (CaA) Zeolite Beads 3. Set 673 K 2. Open 3. Open 1 1) Weight an empty cell. 2) Put approximately 1 g of 5A zeolite beads into the cell. 3) Weigh (sample+cell). 4) Connect the cell to the adsorption measurement instrument. 5) Cover the cell with a heating mantle and increased the temperature to 673 K under vacuum. Maintain the temperature at 673 K for 4 h. 6) After 4 h, remove the heating mantle and cool down. Backfill the cell with helium gas up to about 1 atm. 7) Weigh (degassed sample+cell). 8) Calculate the weight of degassed sample. 9) Connect the cell again to the adsorption measurement instrument and evacuate again. Experiment 1. Degassing 5A (CaA) Zeolite Beads 1. Set 298 K Cool down 3. Backfill with He 2. Close 4. Close 5. Weight 1) Weight an empty cell. 2) Put approximately 1 g of 5A zeolite beads into the cell. 3) Weigh (sample+cell). 4) Connect the cell to the adsorption measurement instrument. 5) Cover the cell with a heating mantle and increased the temperature to 673 K under vacuum. Maintain the temperature at 673 K for 4 h. 6) After 4 h, remove the heating mantle and cool down. Backfill the cell with helium gas up to about 1 atm. 7) Weigh (degassed sample+cell). 8) Calculate the weight of degassed sample. 9) Connect the cell again to the adsorption measurement instrument and evacuate again. Experiment 1. Degassing 5A (CaA) Zeolite Beads 1. Open 2. Open 1) Weight an empty cell. 2) Put approximately 1 g of 5A zeolite beads into the cell. 3) Weigh (sample+cell). 4) Connect the cell to the adsorption measurement instrument. 5) Cover the cell with a heating mantle and increased the temperature to 673 K under vacuum. Maintain the temperature at 673 K for 4 h. 6) After 4 h, remove the heating mantle and cool down. Backfill the cell with helium gas up to about 1 atm. 7) Weigh (degassed sample+cell). 8) Calculate the weight of degassed sample. 9) Connect the cell again to the adsorption measurement instrument and evacuate again. Experiment 2. Determining Vtot and Vcell 3. Open 1. Close 2. Close 1) Fill the helium in the manifold up to ~1 atm (P). 2) Open the valve connecting the manifold and sample cell. 3) After equilibration, check the equilibrium pressure, P`. 4) Calculate the Vtot and Vcell by using equations, PVm = P`Vtot and Vtot = Vm + Vcell (Vm is a known value.) 5) Evacuate the cell and manifold again. Experiment 2. Determining Vtot and Vcell 1) Fill the helium in the manifold up to ~1 atm (P). 2) Open the valve connecting the manifold and sample cell. 3) After equilibration, check the equilibrium pressure, P`. 4) Calculate the Vtot and Vcell by using equations, PVm = P`Vtot and Vtot = Vm + Vcell (Vm is a known value.) 5) Evacuate the cell and manifold again. 1. Open Experiment 2. Determining Vtot and Vcell 1) Fill the helium in the manifold up to ~1 atm (P). 2) Open the valve connecting the manifold and sample cell. 3) After equilibration, check the equilibrium pressure, P`. 4) Calculate the Vtot and Vcell by using equations, PVm = P`Vtot and Vtot = Vm + Vcell (Vm is a known value.) 5) Evacuate the cell and manifold again. 1. Open 2. Open Experiment 3. Measuring Adsorption-Desorption Isotherms <Adsorption> 1) Fill n-butane or iso-butane gas in the manifold up to your desired pressure. if the equilibrium pressure < 0.3 atm, 0.6 atm if the equilibrium pressure > 0.3 atm, (equilibrium pressure in the earlier cycle + 0.3 atm) 1. Close 2. Close 3. Open 2) Open the valve that connects the manifold and the cell. 3) After 5 min equilibration, record the final equilibrium pressure. 4) Close the valve that connects the manifold and the cell 5) Repeat (1-4) until the final equilibrium pressure becomes ~1 atm. Experiment 3. Measuring Adsorption-Desorption Isotherms <Adsorption> 1) Fill n-butane or iso-butane gas in the manifold up to your desired pressure. if the equilibrium pressure < 0.3 atm, 0.6 atm if the equilibrium pressure > 0.3 atm, (equilibrium pressure in the earlier cycle + 0.3 atm) 1. Open 2) Open the valve that connects the manifold and the cell. 3) After 5 min equilibration, record the final equilibrium pressure. 4) Close the valve that connects the manifold and the cell 5) Repeat (1-4) until the final equilibrium pressure becomes ~1 atm. Experiment 3. Measuring Adsorption-Desorption Isotherms <Adsorption> 1) Fill n-butane or iso-butane gas in the manifold up to your desired pressure. if the equilibrium pressure < 0.3 atm, 0.6 atm if the equilibrium pressure > 0.3 atm, (equilibrium pressure in the earlier cycle + 0.3 atm) 1. Close 2) Open the valve that connects the manifold and the cell. 3) After 5 min equilibration, record the final equilibrium pressure. 4) Close the valve that connects the manifold and the cell 5) Repeat (1-4) until the final equilibrium pressure becomes ~1 atm. Experiment 3. Measuring Adsorption-Desorption Isotherms <Desorption> 1) Remove n-butane or iso-butane gas in the manifold down to your desired pressure by using a vacuum pump. if the equilibrium pressure > 0.3 atm, 0.2 atm if the equilibrium pressure < 0.3 atm, 0 atm 1. Open 2) Open the valve that connects the manifold and the cell. 3) After 5 min equilibration, record the final equilibrium pressure. 4) Close the valve that connects the manifold and the cell 5) Repeat (1-4) until the final equilibrium pressure becomes ~ atm. Experiment 3. Measuring Adsorption-Desorption Isotherms <Desorption> 1) Remove n-butane or iso-butane gas in the manifold down to your desired pressure by using a vacuum pump. if the equilibrium pressure > 0.3 atm, 0.2 atm if the equilibrium pressure < 0.3 atm, 0 atm 1. Open 2) Open the valve that connects the manifold and the cell. 3) After 5 min equilibration, record the final equilibrium pressure. 4) Close the valve that connects the manifold and the cell 5) Repeat (1-4) until the final equilibrium pressure becomes ~0.2 atm. Experiment 3. Measuring Adsorption-Desorption Isotherms <Desorption> 1) Remove n-butane or iso-butane gas in the manifold down to your desired pressure by using a vacuum pump. if the equilibrium pressure > 0.3 atm, 0.2 atm if the equilibrium pressure < 0.3 atm, 0 atm 1. Close 2) Open the valve that connects the manifold and the cell. 3) After 5 min equilibration, record the final equilibrium pressure. 4) Close the valve that connects the manifold and the cell 5) Repeat (1-4) until the final equilibrium pressure becomes ~0.2 atm. Questions
© Copyright 2024