Influence of the gas-liquid mass transfer on molecular weight and chemical composition distributions of polymer in slurry polymerization reactors ADRIANO G. FISCH (10/4/2017)

Ch.01 INTRODUCTION

Surface-aeration mode INTRODUCTION 01 Chapter Slurry polymerization technology Multiphase process Solid, liquid and gas phases Stirred tank Loop-tubular Gas dissolution in liquid phase Bubbling mode Surface-aeration mode

01 Mass transfer scheme Slurry reactor INTRODUCTION 01 Chapter Mass transfer scheme Slurry reactor Bubbling mode of gas dissolution (e.g., industrial and pilot plants) Gin Surface-aeration mode (e.g., lab reactors)

Slurry polymerization technology INTRODUCTION 01 Chapter Polymer structure (MWD and CCD) Catalyst nature Slurry polymerization technology Gas dissolution mode Reactor conditions

INTRODUCTION 01 Chapter RESEARCH QUESTION How the gas dissolution mode affects the chemical structure of the polymer? OBJECTIVE To study the mass transfer mechanism and equilibrium concentration of gases in slurry polymerization using bubbling and surface-aeration mode of gas dissolution

Ch.02 MODELING

MODELING 02 Chapter Dynamic model implemented in MatLab

Ch.03 RESULTS AND DISCUSSION

ETHYLENE PARTIAL PRESSURE AND H2/C2 RESULTS AND DISCUSSION 03 Chapter ETHYLENE PARTIAL PRESSURE AND H2/C2 KB2L x ppC2 x H2/C2 Conversions XC2= 0.998 XH2= 0.348 KG2L=10-3 s-1

ETHYLENE PARTIAL PRESSURE AND C4/C2 RESULTS AND DISCUSSION 03 Chapter ETHYLENE PARTIAL PRESSURE AND C4/C2 KB2L x ppC2 x C4/C2 Conversions XC2= 0.998 XC4= 0.982 KG2L=10-3 s-1

BUBBLING  SURFACE AERATION RESULTS AND DISCUSSION 03 Chapter BUBBLING  SURFACE AERATION Partial pressure of ethylene is low Partial pressure of ethylene is high Gin

High partial pressures Concentrations are similar RESULTS AND DISCUSSION 03 Chapter EQUILIBRIUM ethylene 1-butene hydrogen Surface aeration High partial pressures Concentrations are similar Bubbling Low partial pressures

RESULTS AND DISCUSSION 03 Chapter

RESULTS AND DISCUSSION 03 Chapter

CASCADE POLYMERIZATION PROCESS RESULTS AND DISCUSSION 03 Chapter CASCADE POLYMERIZATION PROCESS R1 Good bubbling: KG2L= 10-3 s-1 KB2L= 1 s-1 R2 Poor bubbling: KG2L= 10-3 s-1 KB2L= 10-2 s-1 MWD and CCD of POLYMER HOMOPOLYMER COPOLYMER

03 + H2 flow rate + H2 flow rate + C4 flow rate RESULTS AND DISCUSSION 03 Chapter POLYMER STRUCTURE: MWD AND CCD R1 R2 + H2 flow rate + C4 flow rate + H2 flow rate Maintaining catalyst activity and ethylene partial pressure (same catalyst flow rate)

POLYMER STRUCTURE: MWD AND CCD RESULTS AND DISCUSSION 03 Chapter POLYMER STRUCTURE: MWD AND CCD R2 + H2 flow rate + C4 flow rate CC2= 11 mol.m-3 CH2= 0.83 mol.m-3 CC4= 22.9 mol.m-3 CC2= 11 mol.m-3 CH2= 0.15 mol.m-3 CC4= 6.5 mol.m-3

POLYMER STRUCTURE: MWD AND CCD RESULTS AND DISCUSSION 03 Chapter POLYMER STRUCTURE: MWD AND CCD Good bubbling: KG2L= 10-3 s-1 KB2L= 1 s-1 Poor bubbling: KG2L= 10-3 s-1 KB2L= 10-2 s-1 Maintain the reactant concentration

POLYMER PROPERTIES: MWD AND CCD RESULTS AND DISCUSSION 03 Chapter POLYMER PROPERTIES: MWD AND CCD R2 Good bubbling ppC2= 0.1662 bar H2/C2= 0.1413 C4/C2= 0.0564 Poor bubbling ppC2= 0.8790 bar H2/C2= 0.0270 C4/C2= 0.0155

03 To maintain the reactant concentration ! RESULTS AND DISCUSSION 03 Chapter RELATIONSHIP To maintain the reactant concentration ! To maintain the POLYMER STRUCTURE !

Ch.04 CONCLUSIONS

04 1. MASS TRANSFER INFLUENCES MWD AND CCD; CONCLUSIONS 04 Chapter 1. MASS TRANSFER INFLUENCES MWD AND CCD; 2. H2/C2 AND C4/C2 USING BUBBLING MODE FOR GAS DISSOLUTION ARE LOWER THAN THOSE USING SURFACE-AERATION MODE; 3. FOR MOST POLYMERIZATION PROCESS CONDITIONS, THE SCALING LAW BETWEEN DIFFERENT REACTORS CONCERNING MASS TRANSFER IS THE CONCENTRATION IN SLURRY PHASE; FUTURE WORKS: HOW THE HEAT TRANSFER INFLUENCES MWD AND CCD; EXTENTION OF MODEL CONSIDERING MULTISITE CATALYSTS;

Thank you! Porto Alegre October, 4-5, 2017