Nghiên cứu mô phỏng và tối ưu hóa thiết bị tạo khí nitơ PSA - Phạm Văn Chính

MINISTRY OF EDUCATION AND TRAINING MINISTRY OF NATIONAL DEFENCE ACADEMY OF MILITARY SCIENCE AND TECHNOLOGY ------------------ PHAM VAN CHINH INVESTIGATION OF SIMULATION AND OPTIMIZATION FOR NITROGEN GAS GENERATOR USING PRESSURE SWING ADSORPTION PhD THESIS IN TECHNIQUE Hanoi – 2021 MINISTRY OF EDUCATION AND TRAINING MINISTRY OF NATIONAL DEFENCE ACADEMY OF MILITARY SCIENCE AND TECHNOLOGY ------------------ PHAM VAN CHINH INVESTIGATION OF SIMULATION AND OPTIMIZATION FOR NITROGEN GAS GENERATOR USING PRESSURE SWING ADSORPTION Specialization: Chemical Engineering Code: 9520301 PhD THESIS IN TECHNIQUE Supervisors: 1. Vu Dinh Tien 2. Le Quang Tuan Hanoi – 2021 i COMMITMENT I hereby declare that this is my own research. The research results presented in the thesis and is completely honest.

Scientific conclusions have never been published in any other work by any authors, reference data are fully cited. March, 19th , 2021 PhD Candidate Pham Van Chinh ii ACKNOWLEDGEMENTS First of all, I would like to express my sincere gratitude to my supervisors Associate Professor. Vu Dinh Tien and Dr. Le Quang Tuan for their enthusiastically guidance and helping me to complete this thesis.

They sincere cooperation at every stage of my research work, their valuable advice and assistance always guided me to conduct my research smoothly. Secondly, I would like to thank Head of Academy of Military Science and Technology, Training Department of Academy of Military Science and Technology, Head of Institute of Chemistry - Materials, Department of Physical Chemistry, Department of Machinery and Equipment for Chemical Industrial, School of Chemical Engineering, Hanoi University of Technology, Head of Institute of Technology/General Department of Defense Industry, Department of Chemical Technology have always enthusiastically guided and helped me in all aspects of the thesis implementation process. Finally, I am in debt of my families, friends and relatives for their love and encouragement and motivation in the process of implementing the thesis. PhD Candidate Pham Van Chinh iii TABLE OF CONTENTS Page NOMENCLATURE .vi LIST OF TABLES .xi LIST OF FIGURES.1 Air composition and separation technichques .2 Air separation techniques .1 Introduction of adsorption and adsorbent .2 Molecular sieve adsorbent .3 Theoretical background of adsorption, desorption and nitrogen gas generator using pressure swing adsorption.1 Theoretical background of adsorption and desorption processes.2 Structure of adsorption column .3 Mechanism of adsorption process .4 Structure and principle of N2 gas generator using pressure swing adsorption.4 Mathematical model, simulation and optimization for a single fixed bed.1 Mathematical models to describe a single fixed bed .2 Simulation for process and equipment in adsorption .3 Optimization of nitrogen gas generator .5 The results recently.1 In the world .45 CHAPTER II - OBJECTS AND METHODOLOGY .1 Object and scope .2 Materials, chemicals and equipment .1 Carbon Molecular Sieve .2 Analytical equipment for investigating characteristics of adsorbent .3 A complete experimental system is N2 gas generator using PSA cycle.3 Studying method about carbon molecular sieve .4 Methods of a building experimental systems for air separator by PSA .5 Determining method of diffusion coefficient .6 Determining method of pressure drop through particle layer of a bed .7 Methods establish a mathematical models to describe a single fixed bed 57 2.8 Simulation and optimization of air separator .10 Method scale-up of industry .64 CHAPTER III - RESULTS AND DISCUSSION.1 Specifications of CMS-240 .1 Some general specifications of CMS-240 .2 Thermal analysis DSC and TG of CMS-240.3 Composition and structure of CMS-240.4 Specific surface of CMS-240.2 Manufacturing an experimental system to separate nitrogen gas from air .1 Calculation characteristics and basic dimensions of a single fixed bed .2 Maximum adsorption capacity calculation of a single fixed bed .3 Manufacturing an experimental system to generate nitrogen gas .3 Calculation, measure and analyze pressure drop of particle layer .4 Mathematical models describe a single fixed bed by partial pressure .5 Determine velocity and diffusion coefficient.1 Velocity of air flow through a single fixed bed, uc (m/s) .2 Molecular diffusion coefficient, DAB (cm2/s) .3 Determination membrane diffusion coefficient (Knudsen), Dk (cm2/s) .4 Axial diffusion coefficient, DL (cm2/s) .6 Summary parameters of nitrogen gas generator .7 Simulation and optimization for nitrogen gas generator.1 Simulation and optimization for a single fixed bed.2 Investigation of simulation and optimization for N2 gas generator using PSA.3 Simulation and experimental comparision of a single fixed bed and two beds .8 Scale-up industry for equipment and applications .1 Scale-up industry for equipment with different productivity .2 Application of N2 gas generators for production of RDX explosive.

157 THE SCIENTIFIC PUBLICATIONS. 163 vi NOMENCLATURE ai,1 Coefficient a1 isothermal bi-Langmuir of component i [-] ai,2 Coefficient a2 isothermal bi-Langmuir of component i [-] bi,1 Coefficient b1 isothermal bi-Langmuir of component i [l.g-1] bi,2 Coefficient b2 isothermal bi-Langmuir of component i [l.g-1] DL Axial diffusion coefficient (adsorption bed) [cm2.phút-1] Dia Diameter of bed [cm] F Feed raw materials into bed Nm3/ph, L/ph IP1 Isothermal constant 1 in Aspen Adsorption [-] IP2 Isothermal constant 2 in Aspen Adsorption [-] ki Mass transfer coefficient of component i [1s-1] Ki Equilibrium constant of the component i [-] L, H Height of bed [m] Z Axial distance across bed (from top to bottom of bed) [m] ΔP Pressure drop [bar] ΔPi Partial pressure drop of component i [bar] Pe Standard number Peclet of adsorbent particles [-] qi Amount of gas absorbed in adsorbent of component i [g.g-1] Amount of gas absorbed in adsorbent of component i in q*i [g.g-1] equilibrium rp Particle radius [µm] S Cross-sectional area of bed [cm2] Vbed Volume of bed [cm3] U Theoretical velocity of air flow [m.s-1] vii VDj Volume of dead zone in bed [cm3] XFac Volume correction factor [-] ΔPj Pressure drop in partial j [bar] ΔPmax Maximum pressure drop through bed [bar]  m3void  VT Total empty column volume  m3     m void  3 Vx Empty volume between particles  m3     m3void  Vp Empty volume inside particles  m3     m void  3 εi Intergranular porosity (internal porosity)  m3     m3void  εp Porosity inside particles (particle porosity)  m3     m3void  εt Internal and intergranular porosity (total porosity)  m3    µ Viscosity of liquids, gases [cP]3 ψ Coefficient of particle shape [-]  bar.min  ϕ Pressure drop coefficient  cm 2  [mmHg, P Pressure of gas kG/cm2] V Volume of gas [m3] T Absolute temperature of gas [K] 2,153 Rk Constant of dry air [mmHg.K] 3,461 Rhn Constants of water vapor [mmHg.K] Ci Concentration of component i in gas mixture [mol/cm3] t Time [s] viii U Velocity inside bed [m/s] ρb Buld density of adsorbent [g/cm3] ρp Particle density of adsorbent [g/cm3] ρs Solid density of adsorbent [g/cm3] KL Coefficient of thermal conductivity along axis [J/cm.K] T Temperature [K] Tw Temperature of wall [K] Tatm Temperature of ambient [K] ρg Density of gas [g/cm3] ρb Bulk density of adsorbent [g/cm3] ρw Density of wall material [g/cm3] Cpg Specific heat capacity of gas [J/g.K] Cps Specific heat capacity of adsorbent [J/g.K] Cpw Specific heat capacity of wall material [J/g.K] [J/mol ΔH Thermal effect of adsorption process ] hi Coefficient of internal heating [J/cm2.s] ho Coefficient of external heating [J/cm2.s] RBi The inner diameter of bed [cm] RBo Diameter outside of bed [cm] Rp Diameter of particle [cm] Aw Cross-sectional area of wall [cm2] B Parameter equations Langmuir extended [kPa-1] qm Equilibrium parameter for extended Langmuir equation [mol/kg] ix Pi Pressure of component i [kPa] K Coefficient of Langmuir equation expand - ω LDF coefficient [s-1] De Diffusion coefficient of component in solids [cm2/s] Pr Pressure drop coefficient according to size. - Re Standard number Reynol - AAS Atomic Absorption Spectrometer ACF Actived Cacbon Fiber BET Brunauer –Emmet-Teller CA Controlled Atmosphere CMS Cacbon Molecular Sieves CO Certificate Original CQ Certificate Quality DNA Deoxyribonucleic acid DSC Differential Scanning Calorimeter DTA Differntial Thermal Analysis EDX Energy Dispersive X-ray GAC Granular Actived Cacbon IQF Individual Quick Freezer ITM Ion Transport through Membranes LDF Linear Driving Force MMSCFD Million standard cubic feet of gas per day x MAP Modified Atmosphere Packaging MTZ Mass transfer zone PSA Pressure Swing Adsorption PAC Powdered Actived Cacbon PLC Programphg Logic Controler RNA Ribonucleic acid RDX Cyclotrimetylenethylene trinitriaphe SCFD Standard cubic feet per day (gas) SMR Steam methane reforphg SMB Simulation Moving Bed SCADA Supervisory Control and Data Acquisition SEM Scanning Electron Microscope FE-SEM Field Emission Scanning Electron Microscopy TEM Transmission electron microscope TG Thermogravimetry TSA Temperature Swing Adsorption VSA Vaccum Swing Adsorption VOC Volatile Organic Compounds xi LIST OF TABLES Page Table 1. 1 Applications of adsorbents.

2 Characteristics of zeolites [19]. 3 Product quality specification of some CMS. 4 Principle of N2 gas generator. 1 Section dimension of some gases [8].

1 Moisture and densities results of CMS-240. 2 Characteristics summary table of a single fixed bed. 3 Results of pressure drop through a single fixed bed using PSA cycle. 4 Comparative mathematical models describing adsorption and desorption processes in gas and solid phases, respectively.

5 Calculation results of axial diffusion coefficient DL. 6 Synthesizes parameters of N2 gas generator. 7 Setup parameters to investigate for a single fixed bed. 8 Simulation and experimental comparision for a single fixed bed.

9 Parameters setting for two bed, 4-step. 10 Investigation for two beds 4-step (Skarstrom). 11 Evaluation and comparison between a single fixed bed and two beds at feed pressure 5 bar. 12 Parameters of 6-step cycles (Berlin).

13 Comparing of simulation and experimental, optimize for two beds. 14 Scale-up industry results for N2 gas generators by calculation and simulation. 152 xii LIST OF FIGURES Page Figure 1. 1 Diagram compositions of air in the atmosphere.

2 Diagram P&ID technology of gas separation line by cryogenic air separation industrial. 3 Diagram P&ID gas separation by membrane. 4 Diagram of PSA and TSA cycles principle. 5 Diagram P&ID of gas separator by PSA cycle.

6 Diagram P&ID of gas separator by TSA technology. 7 Diagram P&ID of gas separator by VSA technology. 8 Structural evolution from primary block AlO4 or SiO4 to a type of sodalite (also known as β-cage) secondary structure and finally structures of some typical types of zeolite such as type A, X and Y. 9 Porous structure of carbon molecular sieve and formation.

10Adsorption equilibrium lines of N2 and O2 on CMS carbon molecular sieve at 25°C [106]. 11 Micropore dimensions of some adsorbents and molecular sizes of components [98]. 12 Diagram of langmuir adsorption mechanism on a plane. 13 Effect of factors on Langmuir isothermal relation.

14 Description of structure of a single fixed bed of N2 gas generator using pressure swing adsorption and carbon molecular sieve. 15 Adsorption mechanism of O2 molecule to CMS adsorbent particle. 16 Structure and principle of N2 gas generator using PSA. 17 Model of adsorption column according to PSA cycle.

18 Experimental system of equipment generating N2 by PSA cycle. 19 Diagram of nitrogen gas generator based on Aspen Adsorption. 1 A elemental of a single fixed bed. 1 Analysis results of particle size distribution.

2 Thermal analysis results DSC and TG of CMS-240 sample. 3 SEM image 1x10 times of CMS-240 sample .000 times of inside CMS-240. 5 SEM photo1x50,000 times of inside CMS-240. 6 FE-SEM image 1x200K of inside CMS-240 particle.

7 Detecting position of coating layer of material particle. 8 X-ray diffraction spectra of EDS-JED 2300 probe. 9 Location at internal layer of adsorbent particles. 10 X-ray diffraction spectra of EDS – JED 2300 probe.

11 P&ID diagram of a single fixed bed model. 12 P&ID diagram of N2 gas generator using PSA cycle. 13 Nitrogen gas generator using PSA. 14 Parameter setting window.

15 Monitor, control and collect data by SCADA window. 16 Window to observe changing of technology parameters. 17 Window to print and export study data .