LABoratory Nanomaterials

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Adsorption, Modeling, LABoratory Nanomaterials Supervisor: Professor Shohreh Fatemi School of Chemical Engineering College of Engineering University of Tehran

Contents Introduction....1 People..2 Industrial Projects...3 Numerical Modeling Packages..5 Products.. 7 Lab. Equipments.. 24

Introduction Adsorption and reactive process of gas and/or liquids in heterogeneous systems and mathematical modeling and optimization of the related processes are the activities of this laboratory. Some of the activities are focused on formation of the fine layers, as core-shell catalysts, membrane fabrication and modeling their properties. The methods of testing adsorbents, related properties and membranes need different equipments and facilities and this lab is working on set-up these systems. Synthesis and production of some nano-structured materials, nanoparticles, nano-films and nano-photocatalysts are taken place in this lab and their properties are determined experimentally. The catalytic properties as well as adsorptive properties of the produced materials are investigated and modeled in heterogeneous systems. Mathematical modeling, simulation and optimization of the adsorption processes, heterogeneous reactors (fixed beds, trickle beds, moving beds, bubble columns, fluidized, slurry, and membrane reactors) are performed for refining natural gas and oil, environmental issues, CO2 fixation, hydrogen purification, and production high-value products, in this lab. 1

People Professor Shohreh Fatemi Professor, Faculty member of School of Chemical Engineering, College of Engineering, University of Tehran, Tehran, Iran P.O. Box: 11155-4563, Tehran, Iran Phone: +982161112229 Tel/Fax: +982166957784 Cell Phone: +989122079745 E-mail: shfatemi@ut.ac.ir INTERESTED RESEARCHES Mathematical Modeling of Catalytic Reactions in Gas and Oil Processes Mathematical Modeling and Simulation of Adsorption Processes Synthesis of Nano Materials and Application in Catalytic and Adsorption Processes Application of Supercritical CO2 in Preparation Pharmaceutical Materials and Nano Particles Synthesis and Application of Photo Catalysts in Energy and Environment Membrane and Hydrogen Purification Processes AWARD AND ACHIEVEMENTS The Distinguished Applicable Project in 24 th Research Festival 2015, University of Tehran. The Distinguished Researcher in 23 rd Research Festival 2014, University of Tehran. The District Researcher in 19 rd Research Festival 2010, University of Tehran. The District Research Project Applied in 18 rd Research Festival 2009, University of Tehran, Subjected by: "Investigation of Nano-Structured Carbon Materials for Capturing and Storage of Natural Gas". Award of Prevalent Advisory of the Research Projects in Research Institute of Petroleum Industry in 2008. Award of the first Top Graduated Student of M.Sc. Chemical Engineering in Faculty of Engineering, University of Tehran. 2

Industrial Projects Control Modeling of Cyclic Pressure Swing Adsorption for Separation of He from Natural Gas, National Iranian Gas Company (NIGC), 2016. Simulation of Separation and Purification of He from Natural Gas by Cyclic Pressure Swing Adsorption, National Iranian Gas Company (NIGC), 2016. Design and Simulation of a Cyclic Temperature Adsorption Process for Separation of Gas condensate from Natural Gas, Persian Gas Company, 2016. Simulation Study of CO2-H2O Co-adsorption in Natural Gas Dehumidification Process in Refinery by 4A Molecular Sieve and Suggestions, Persian Gas Company, 2016. Study and Modeling the Zeolitic Membrane behavior for Light Gases Separation (Carbon Dioxide from Natural Gas), National Iranian Gas Company (NIGC), 2013. Fabrication and Modification of ZSM-5 Nano-structured Zeolite for the Process of Dehydrogenation of Propane, Iran National Science Foundation (INSF), 2013. Modeling and Simulation Software Package for Liquid and Gas Adsorption Processes, Vice Chancellor for Research, University of Tehran, 2013. Technical Knowledge for Production of Photocatalytic Papers from Enhanced TiO2 for Reduction of Environmental Pollutants, Ministry of Industry, Mine and Trade, 2012. Modeling and Dynamic Simulation of the Industrial Hydro-treating Process of Oil Cuts in Trickle bed Reactors and Optimization of the Operational Conditions to Minimize the Outlet Sulfur Concentration, National Iranian Oil Refining & Distribution Company (NIORDC), 2011. Mathematical Modeling and Simulation of Cyclic Pressure Swing Adsorption Process for Purification of Hydrogen from the Reforming Process gaseous Products, National Iranian Oil Refining & Distribution Company (NIORDC), 2011. Fabrication of Tubular Membrane from Silico-Aluminophosphate Structures and Application Study for Light Gaseous Mixtures, Ministry of Industry, Mine and Trade, 2011. Synthesis and Characterization of Silico-Aluminophosphate Molecular Sieve, Iran National Science Foundation, 2011. 3

Investigation of Separation outlet Gases from OCM Reaction by Molecular Sieves for Yield Enhancement of C2 Products, Petrochemical Research and Technology Company, 2009. Mathematical Modeling and Simulation of Absorption Process for Separation of the outlet Gases from the OCM Reaction by Molecular Sieves, Petrochemical Research and Technology Company, 2009. Investigation of Adsorption Capacity and Storage of Natural Gas (Methane) in Carbon Nanostrutured Materials, National Iranian Gas Company (NIGC), 2007. Production of Water-Based Traffic Paint applied for Intermediate Climates, Industrial Development and Renovation Organization of Iran (IDRO), 2006. Investigation of Separation of Zirconium and Hafnium Cations by Ion Exchange Chromatographic Method, Iran National Science Foundation, 2006. 4

Numerical Modeling Packages Numerical Simulation of Commercial Natural Gas Dehydration Process established in Parsian Gas Refinery. Kinetic Modeling of Benzene Alkylation Process to Achieve Alkyl Aromatics in Presence of Heterogonous Zeolytic Catalysts. Dynamic Modeling of Nano Carbon Adsorption Beds for Adsorption and Separation of Gaseous Pollutants from Synthesis Gas. Modeling and Simulation of Claus Sulfur Recovery Unit. CFD Modeling of the Packed bed Reactors for CO2 Adsorption from Natural Gas by Molecular Sieves. CFD Modeling of the Spouted bed Reactors for VOC Removal by Nano Photocatalytic TiO2 Particles. Kinetic Modeling of PDH (Propane Dehydrogenation) Reaction on Modified SAPO-34. Mathematical Modeling of Oxidative Propane Dehydrogenation Process in the Side Feeding Reactors. Gibbs-Excess Thermodynamic Modeling of Gaseous Mixture Adsorption on Nano Adsorbents. Kinetic Modeling of VOC Photocatalytic Reactions on Nano Titania. Modeling and Optimization of Dynamic Adsorption Process by Core-shell Adsorbents for Separation of Light Gases. Modeling and Simulation of Temperature-Pressure Swing Adsorption Process for Enrichment of Methane in Natural Gas by Zeolitic Adsorbents. Modeling and Simulation of Hydro desulfurization Process of Diesel in Commercial Trickle Bed Reactor. Modeling and Simulation of Pressure Swing Adsorption of Commercial Process for Hydrogen Purification (Separation from Syngas-Naphtha Reforming outlet Gas). Modeling and Simulation of Methane Steam Reforming and Dry Steam Reforming in Fixed Bed Reactors, Membrane Reactors and Fluidized Bed Reactors. 5

Modeling and Simulation of Naphtha Reforming of Commercial Processes (Semi-regenerative and Continuous Catalytic Regeneration). Kinetic Modeling of Methanol to Olefins Process by Silico-Aluminophosphate-34 Catalyst. Kinetic Modeling of Heavy Oil Hydro-cracking Reaction in Catalytic Packed Bed Reactors. Modeling and Simulation of Pressure Swing Adsorption and Temperature Swing Adsorption Process for Separation of Methane from Ethane and Ethylene Mixture. Modeling and Simulation of Fischer-Tropsch Reaction of Syngas in Bubble Slurry Reactors. Modeling and Simulation of Multi-component Dynamic Adsorption Process for Separation of Gases and Liquids. Mathematical Modeling of Essential Oil Extraction from Pharmaceutical Plants by Supercritical Extraction. 6

Products T type Zeolite - Used as a Molecular Sieve in the Adsorption and Separation of Air and Carbon Dioxide from Natural Gas and Membrane Processes Characterization: - XRD of T type Zeolite 9000 8000 7000 6000 Intensity 5000 4000 3000 2000 1000 0 5 10 15 20 25 30 35 40 2theta - SEM photograph of T type Zeolite 7

SAPO-34 Membrane - Used as a Membrane in Separation of Light Gases Characterization: - XRD of SAPO-34 Membrane - SEM photograph of SAPO-34 Membrane on Ceramic Support (Right: Top Section, Left: Cross Section) 8

SAPO-34 Particulate - Used As A Molecular Sieve in the Separation of Light Gases Such As Methane from Impurities - Used As Nano-structured Catalyst in the Process of Converting Methanol to Light Olefins Characterization: - XRD of SAPO-34 Particulate - SEM photograph of SAPO-34 Particulate 9

TiO2 Nano Particle - Photocatalyic Reaction - Membrane Photocatalytic Reaction Characterization: - XRD of TiO2 Nano Particle - SEM photograph of TiO2 Nano Particle 10

Zeolite 5A Nano Particle - Adsorbent - Membrane Characterization: - SEM photograph of Zeolite 5A Nano Particle 11

Photocatalytic Paper made of Activated Nano Titania in Visible Light - Removal of VOC from the Air Characterization: - XRD of Enhanced TiO2 Activated in Visible Light (a) - Activity Tests of VOC removal in Visible Light by Photocatalytic Paper (b) (a) (b) - SEM photograph from the Surface of the Composited Paper with Modified Nanotitania 12

Growth of Carbon Nano Fibers by Natural Gas on the Surface of Activated Carbon - To Produce Enhanced Carbon Adsorbents for deep Desulfurization from Oil Cuts - An Adsorption unit to be used in downstream of Hydrotreating Process for Adsorption of Sulfur Compounds from Diesel (Reduction of Sulfur to 50 ppm) Characterization: - SEM photograph with a magnification of 2000, Carbon Nano Fibers grown on the Surface of Activated Carbon without any Catalyst - SEM photograph with a magnification of 2000, Carbon Nano Fibers grown on the Surface of Activated Carbon with Catalyst 13

ZSM-5 Zeolites - Used for the Process of Propane Dehydrogenation and Propylene Production. Characterization: - XRD of ZSM-5 Zeolites - SEM photograph of ZSM-5 Zeolites 14

ZSM-5 Zeolites (Continued) - FESEM photograph of ZSM-5 Zeolites 15

Core-Shell Catalysts Made of SAPO-34 and ZSM-5 - Used for Light Olefins Production. Characterization: - XRD of Core-Shell Catalysts Made of SAPO-34 and ZSM-5 (Shell ZSM-5 on Core SAPO-34) - FESEM photograph of Core-Shell Catalysts Made of SAPO-34 and ZSM-5 16

Hierarchical SAPO-34 - Tuned Pore Size SAPO-34 from Micropore to Mesopore Structure, Used for Preventing Coke Formation in Catalytic Reactions. Characterization: - XRD - SEM photograph Conventional SAPO-34 Hierarchical SAPO-34 17

Hierarchical SAPO-34 (Continued) - Adsorption-Desorption Isotherms Conventional SAPO-34 Hierarchical SAPO-34 18

Graphene oxide (GO) - Nano Drug Loading, Dipping with TiO2 for Photocatalytic Activity Enhancement, Third Regeneration of Solar Cells, Characterization: - XRD Synthesized GO (Red Color) and Graphite Source (Blue Color) - TEM photograph 19

TiO2 Nanotubes (TNT) and Cu-doped TiO2 Nanotubes - Catalytic Oxy-Desulfurization of Fuel Oils Characterization: - XRD - SEM photograph (a) TNP, (b) synthesized TNT and (c) Cu-TNT Cu-TiO2 Nanotubes TiO2 Nanotubes 20

TiO2 Nanotubes (TNT) and Cu-doped TiO2 Nanotubes (Continued) - TEM photograph TiO2 Nanotubes 21

Titano-Silicate Nanostructure - Catalytic Reactions and Adsorption of Sulfur Compounds Characterization: - XRD Wide angle X-Ray patterns of TS-1 Low angle X-Ray patterns of Ti-MCM-41 22

Titano-Silicate Nanostructure (Continued) - SEM photograph SEM image of TS-1 SEM image of Ti-MCM-41 SEM image of Ti-SBA-15 23

Lab. Equipments Gas Chromatography (Type 1) - Gas chromatography (GC) is a common type of chromatography used in analytical chemistry for separating and analyzing compounds that can be vaporized with/without decomposition in detector. Typical uses of GC include identification the type and purity of a particular component in gas or liquid mixture. Specifications: - TCD & FID Detectors - Online/offline Injection - Sampling valve - Hydrogen Generator - Methanizer GC - FID & TCD Detector 24

Gas Chromatography (Type 2) - Gas chromatography (GC) is a common type of chromatography used in analytical chemistry for separating and analyzing compounds that can be vaporized with/without decomposition in detector. Typical uses of GC include identification the type and purity of a particular component in gas or liquid mixture. Specifications: - HID Detector - Online/offline Injection - Sampling valve GC - HID Detector 25

Static and Dynamic Gas Adsorption Apparatus Measurements (Laboratory Setup) - Determination of Adsorbent Selectivity for Different Gases - Determination of Equilibrium Adsorption Capacity of Adsorbents for Various Gases - Determination of Adsorption Isotherms - Determination of Adsorption Parameters Specifications: - Mixing Cells - Adsorption bed - Needle Valves - Mass Flow Controllers - Vacuum Pumps - Heating Jackets - Thermocouples - Pressure Transducer Static and Dynamic Gas Adsorption Apparatus Measurements 26

Stirred Batch Reactor (Laboratory Setup) - Synthesis of fine materials in Liquid Phase Specifications: - Condenser - Inlet and outlet valve - Heating/cooling Jacket - Mixer Stirred Batch Reactor 27

High Pressure Autoclave - Membrane Synthesis - Fine Particle Synthesis - High Pressure Batch Reactor Specifications: - External Agitation System - Teflon lined Stainless Steel Autoclave - Working Pressure up to 100 bar - Working Temperature up to 500 C High Pressure Autoclave System 28

Cata-test Reactor - Kinetic Reaction Studies - Cata-test for Two & Three Phases - Thermal Treatment - CVD Application Specifications: - Temperature Controller (up to 1200 C) - Gas Mass Flow Controller - Liquid Dosing Pump - Tubular Reactor - High Temperature Furnace Cata-test Reactor 29

Photocatalytic Reactor - Photocatalytic Reactions - VOC Decomposition Specifications: - UV/Visible Light Accessories - Heating/Cooling Jacket - Mixing - Batch/Continuous Operation Photocatalytic Reactor 30

Tubular Membrane Module (Laboratory Setup) - Selectivity Tests - Permeability Tests - Gaseous Membrane Application Specifications: - Membrane Module - Online GC - Heating/Cooling Jacket - Mass Flow Controller - Pressure and Temperature Sensor - Back Pressure Regulator - Metering Valve Gases Tubular Membrane Test 31

Two-bed PSA and/or TSA Apparatus (Laboratory Setup) - Adsorption-Desorption Cycle - Separation of Gases - Purification of Gases Specifications: - Pressure Transducer - Temperature Controller - Mass Flow Controller - Stainless Steel Adsorption Columns - Back Pressure Regulator Two-bed PSA and/or TSA Apparatus 32

Solar Simulator Apparatus - Solar simulator (also artificial sun) is a device that provides illumination approximating natural sunlight. The purpose of the solar simulator is to provide a controllable indoor test facility under laboratory conditions, used for the testing of solar cells, sun screen, plastics, and other materials and devices. Solar simulator produces sun light from combination of various wave lengths equipped inside a box with required intensity. The solar devices can be exposed to the simulated solar light in this apparatus and the voltage and amperage can be detected by an I-V instrument. Solar Simulator Apparatus 33

Sonicator - The sonicator has an Ultra-sonic probe for the direct sonication of the liquids. The probe is protected inside a box and can prepare max. 20 khz frequency with max. Power of 40 w. The apparatus is equipped with a touch screen digital control for setting the time of process, power and intensity, and the apparatus has a thermocouple for sensing temperature during process. Sonicators have become the industry standard for: - Dispersing - Deagglomerating - Particle size reduction - Particle synthesis and precipitation - Surface fictionalization. Sonicator 34

Spin-Coater Apparatus - Spin coating is one of the most common techniques for applying thin films to substrates and is used in a wide variety of industries and technology sectors. The advantage of spin coating is its ability to quickly and easily produce very uniform films from a few nanometers to a few microns in thickness, by applying high speed rotation under vacuum. This apparatus has three rotating speed levels; 3000, 6000 and 9000 rpm. Spin-Coater Apparatus 35

Phone: +982161112229 Tel/Fax: +982166967784 Address: School of Chemical Engineering, College of Engineering, Central Campus, University of Tehran, 16th of Azar Street, Enghelab Ave., Tehran, Iran. shfatemi@ut.ac.ir www.amn.ut.ac.ir