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CO2 Absorption Rate Improvement of an Amino Acid Salt Solvent with an Inorganic Promoter

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CO2 Absorption Rate Improvement of an Amino Acid Salt Solvent with an Inorganic Promoter CO2 Absorption Rate Improvement of an Amino Acid Salt Solvent with an Inorganic Promoter vorgelegt von Dipl.-Ing. Diego Andrés Kuettel geb. in Madrid (Spanien) von der Fakultät III - Prozesswissenschaften der Technischen Universität Berlin zur Erlangung des akademischen Grades Doktor der Ingenieurwissenschaften -Dr.-Ing.- genehmigte Dissertation Promotionsausschuss: Vorsitzender: Prof. Dr. Felix Ziegler Gutachter: Prof. Dr. George Tsatsaronis Gutachterin: Prof. Dr. Tetyana Morozyuk Gutachter: Prof. Dr. Klaus Görner Tag der wissenschaftlichen Aussprache: 6. November 2015 Berlin 2016 Table of Contents 1. Introduction ..........................................................................................................................1 1.1. Evolution of Acidic Gas Treatment ...............................................................................................2 1.1.1. Acidic Impurity Removal ...........................................................................................3 1.1.2. Purification of Synthesis Gas ....................................................................................4 1.1.3. Carbon Dioxide Recovery from Combustion Flue Gases .........................................6 1.1.4. Carbon Capture and Storage (CCS) .........................................................................8 1.2. The PostCapTM Process .............................................................................................................9 1.3. Motivation and Scope .................................................................................................................11 2. Basic Principles ..................................................................................................................13 2.1. Gas Absorption ...........................................................................................................................14 2.1.1. Film Theory .............................................................................................................14 2.1.2. Diffusion Rate .........................................................................................................15 2.1.3. Enhancement of Mass Transfer with Chemical Reaction .......................................16 2.1.4. Conventional Chemical Solvents for CO2 Capture .................................................19 2.3. Amine-CO2 Reaction Chemistry ................................................................................................22 2.4. Amino Acid Salt Solvents ...........................................................................................................24 2.4.1. AAS properties ........................................................................................................24 2.4.2. CO2 Absorption with AAS .......................................................................................25 2.4.3. Addition of an Absorption Rate Promoter ................................................................26 2.5. State of the Art CO2 Recovery Plant ..........................................................................................28 2.6. Carbon Capture Performance Variables ....................................................................................30 2.7. Key Operating Variables .............................................................................................................31 2.7.1. Column Packing Height ..........................................................................................31 2.7.2. Solvent Flow Rate ...................................................................................................31 2.7.3. Absorber Operating Temperature ............................................................................31 2.7.4. Solvent Strength .....................................................................................................31 !i 2.8. Carbon Capture Plant Scale-Up .................................................................................................32 3. Absorption Rate Measurement in the Stirred Cell ..............................................................35 3.1. CO2 Absorption Rate Promoters ................................................................................................36 3.1.1. Chemical Properties ...............................................................................................36 3.1.2. Promoter Ranking Criteria ......................................................................................37 3.2. Experiment Setup and Procedure ..............................................................................................38 3.2.1. Experiment Setup ...................................................................................................38 3.2.2. Experiment Procedure ............................................................................................40 3.2.3. Experiment Conditions ............................................................................................41 3.2.4. Results Interpretation ..............................................................................................41 3.3. Solvent Kinetic Measurement..................................................................................................... 43 3.4. Screening Study .........................................................................................................................45 3.4.1. Toxicity ....................................................................................................................45 3.4.2. Promoter Enhancement Factor ...............................................................................46 3.4.3. PROM-1 Solubility ..................................................................................................49 3.4.4. Market Price ............................................................................................................51 3.4.5. Promoter Selection .................................................................................................51 3.5. Further Pressure Drop Experiments ...........................................................................................52 3.5.1. Promoter Enhancement Effect at Different CO2 Loadings ...........................................52 3.5.2. Promoter Enhancement Effect on Other AAS Solvents ..........................................53 3.5.3. Promoter Enhancement Effect with Co-Promoter ...................................................54 3.6. Conclusion ..................................................................................................................................57 4. Rate Promoter Laboratory Testing in the Mini Plant ...........................................................59 4.1. Reboiler Heat Duty for CO2 Desorption .....................................................................................60 4.2. Experiment Setup and Procedure ..............................................................................................63 4.2.1. Siemens Mini Plant .................................................................................................63 4.2.2. Operating Variables ................................................................................................64 4.2.3. Measuring Procedure .............................................................................................65 !ii 4.3. Results and Discussion ..............................................................................................................66 4.4. Conclusion ..................................................................................................................................69 5. Rate Promoter Testing under Real Gas Conditions ...........................................................71 5.1. Pilot Plant vs. Mini Plant .............................................................................................................72 5.2. Experimental Setup and Procedure ...........................................................................................73 5.2.1. Pilot Plant Description .............................................................................................73 5.2.2. Operating Variables ................................................................................................76 5.2.3. Experimental Procedure .........................................................................................76 5.3. Results and Discussion ..............................................................................................................78 5.3.1. Capture Rate ..........................................................................................................78 5.4. Conclusion ..................................................................................................................................80 6. Promoted CCS+ Model Development in Aspen Plus® ......................................................81 6.1. Basics 82 6.1.1. Process Flow Diagram ............................................................................................82 6.1.2. Bravo Rocha Fair 92’ Mass Transfer Correlation ....................................................83 6.1.3. Thermo-physical Properties ....................................................................................83 6.1.4. Chemical Reaction ..................................................................................................84 6.1.5. Column Properties ..................................................................................................84
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