HiPerCap High Performance Capture

Transcription

1 Earl Goetheer, Principal scientist at TNO HiPerCap High Performance Capture Absorption Systems Natural gas Oil Bio-fuel Coal Source CO 2 capture Transport Storage

2 Capture in /06/2012 2

3 Scrubber Absorber Regenerator Lean solvent Challenges Post-combustion Capture Makeup water avoid emission solvent traces CO 2 -lean gas Condenser CO 2 gas Top Tray Rich solvent Top Tray Reflux Reflux drum Pump reduce absorber, scrubber investment advanced heat integration Bottom Tray Bottom Tray Vapor Steam CO 2 -rich gas Rich solvent Lean solvent Liquid Pump Reboiler Condensate reduce heat consumption 21/06/2012 3

4 Emission Volatile emission MEA/[mg/Nm 3 ] Aerosol emission Low Soot High Soot Low level H 2 SO 4 aerosol Middle level H 2 SO 4 aerosol High level H 2 SO 4 aerosol /06/2012 Particle number conc./[1/cm 3 ] 4

5 infiltration air Integration water/steam air flue gas CO2 coal SCR APH infiltration air FF FGD DCC II air coal mill I air PZ process ~ CO2 to storage 21/06/2012 5

6 Energy Consumption Specific energy duty GJ th /t CO 2 21/06/2012 6

7 Technologies Enzymatic catalysed CO2 capture Biomimicking Strong bicarbonate formers Precipitating solvent systems Capture integrated with algae cultivation 21/06/2012 7

8 Precipitating solvent systems 21/06/2012 8

9 CO 2 absorption with amino acid salts Glycine Taurine Resistant to oxidative degradation Less waste generated products Zero emissions of active reactant Potential energy savings Limited solubility in water Ionic equilibria In water: R-(NH 2 )COOH R-(NH 3 ) + COO - zwitterion - H + - H + R-(NH 3 ) + COOH R-(NH 3 ) + COO - R-(NH 2 )+COO - R-(NH 3 ) + COO - + KOH R-(NH 2 )COO - K + reactive 9

10 CO 2 Pressure [Pa] Effect of solid precipitation Enhanced absorption capacity: DECAB principle Combined process No precipitation With precipitation o C ; 6M AmA 0 0,1 0,2 0,3 0,4 0,5 Loading [mole CO 2 /mole AmA) Experimental: Aqueous potassium taurate. Dark points: precipitation From: Kumar et al. Ind. Eng. Chem. Res. 42, 2003, Schematic picture: effect of solvent precipitation 10

11 Why do you get higher capacity? Reactions with CO 2 (similar to normal amine systems): Carbamate formation (primary and secondary amines) CO OOC-R-NH 2 - OOC-R-NH-COO - + -OOC-R-NH 3 + (1) amine carbamate protonated amine Carbamate hydrolysis - OOC-R-NH-COO - + H 2 O - OOC-R-NH 2 + HCO - 3 (2) carbamate amine bicarbonate Bicarbonate formation (tertiary amines, sterically hindered secondary amines) CO OOC-R-NH 2 - OOC-R-NH HCO - 3 (3) amine protonated amine bicarbonate Removed by precipitation 11

12 Working with solids in the process Controlled precipitation of the solvent Solids should appear where they can be handled Equipment selected for solids handling Process complexity increased Working with solids IF there is an economic breakthrough 12

13 DECAB Process (Design & Modelling Results) Clean Gas 504 kg/s Loading 0,13mol/mol HX-3 16MW Pre-loaded solvent Carbon dioxide 36MW Loading 0,33mol/mol Flash vessel Spray column Stripper Absorption column Flue Gas Loading 0,26mol/mol 190 Nm3/s 8vol% 90 C => 50 C 89MW Loading 0,43mol/mol Loaded solvent HX-1 10MW HX-2 76 MW 120 C Loading 0,13 mol/mol 13

14 From DECAB to DECAB+ Conditions to enhance absorption and desorption Absorption: High ph (basicity) Desorption: Low ph (acidity) Clean Gas CO2 to compresion Make up water Lean solvent HX-2 Pre-loaded solvent, particle free Lean solvent Condenser Strip gas Depleted Flue gas Reflux Spray column Loaded solvent, Particle free Stripper Absorption column Loaded solvent, slurry Flue Gas HX-1 14

15 CO2 Partial pressure [bar] CO2 Partial pressure [bar] Effect of DECAB +. Enhanced desorption 10 VLE 80ºC 10 VLE 100ºC 1 1 0,1 0,01 0,001 VLE 4M /4M 80ºC Fit 4M / 4M 80ºC VLE 3.5M / 5M 80ºC Fit 3.5M / 5M 80ºC 0 0,1 0,2 0,3 0,4 0,5 0,6 Loading [mol CO 2 / mol Amino acid] 0,1 0,01 VLE 4M / 4M 100ºC Fit 4M / 4M 100ºC VLE 3.5M / 5M 100ºC Fit 3.5M / 5M 100ºC 0 0,1 0,2 0,3 0,4 0,5 0,6 Loading [mol CO 2 / mol Amino acid] The ph shift increases the partial pressure of CO 2 at a given loading 15

16 Proof of principle CO 2 flask To analyzer Liquid removed Vol (%) Conc. M T C Rich Loading mol/mol Lean Loading mol/mol 0% N 2 21% % Low lean loadings are possible at relatively low temperatures 0% % %

17 Key advantages of DECAB + Low desorption temperature Possibility to use low grade heat / waste heat (Ideal for the refinery case) Possibility to achieve lower lean loadings without increasing reboiler temperature (Ideal for streams with low CO 2 concentrations such as flue gas from gas turbines combustion) High pressure desorption Lower operating costs due to enhanced desorption All environmental advantages from amino acids 17

18 DECAB + Process Concept 18

19 CO2 capture algae cultivation 19

20 21/06/

21 Biomass community Hybrid poplar (Populus spp.) (C3) EXAMPLES OF HIGH PRODUCTIVITY BIOMASS Location Yield (t d.w. ha -1 y -1 ) Photosynthetic efficiency (%) Minnesota Water hyacinth (Eichornia crassipes) Mississippi (>150) Switch grass (Panicum virgatum) (C4) Texas Sweet sorghum (Sorghum bicolor) (C4) Texas-California Coniferous forest England Maize (Zea mays) (C4) Israel Tree plantation Congo Tropical forest West Indies Algae Different locations Sugar cane (Saccharum officinarum) Hawaii-Java Napier grass (Pennisetum purpureum) Hawaii, Puerto Rico M. Tredici. Symposium I Biocarburanti di seconda e terza generazione Roma 14 April /06/

22 21/06/ Per kg dry biomass ~ 4,4 kg of CO2 is needed

23 Scrubber Absorber Regenerator Lean solvent ~75% OPEX is predominantly CO 2 desorption/ solvent regeneration Makeup water CO 2 -lean gas Condenser CO 2 gas ~20% efficiency loss of power plant due to high energy demand for desorption Top Tray Rich solvent Top Tray Reflux Pump Reflux drum Bottom Tray Bottom Tray Vapor Steam CO 2 -rich gas Rich solvent Lean solvent Liquid Pump Reboiler Condensate 21/06/

24 Scrubber Absorber Lean solvent Makeup water Top Tray CO 2 -lean gas Need for major cost reduction of CO 2 capture and limited efficiency loss for power plants and industrial emission sources. Leads to new business models for Algae to biofuels production. Bottom Tray Al Rich solvent Biomass/ products Flue gas 21/06/2012 Rich solvent Lean solvent Algae based Regenerator Pump 24

25 From algae to products improvement options Nutrients/ CO 2 Inoculation Cultivation Harvesting & Processing Valorization Pharmaceutical Industry Advanced Nutrient Delivery Technology. Proteins Animal feed Algae-strain Growing System Closed systems Energy efficient harvesting, extraction and processing system. Oils & hydrocarbons Chemical Industry Biofuels Advanced algal Strain Technology Carbohydrates Electricity generation Open systems Biomass Aquaculture feed 21/06/

26 Advanced algal Strain Technology 21/06/

27 Limitation: Mutual shading Decreased light penetration = Slower growth = Lower biomass density Solution: Light efficient strains Same algal density 1,5 gr/ltr Wild strain Improved Strain Non-GMO 21/06/2012 Max. algal cell density of 8 gr/ltr for 27 Light Efficient Strain

28 Advanced Nutrient Delivery Technology. 21/06/

29 Efficient CO 2 -nutrient feeding Current state-of-the-art Pure CO 2 bubbling Flue gas washing/bubbling (diluted CO 2 stream) 21/06/

30 Two possible routes researched at TNO Enzyme promoted CO 2 capture Carbonic Anhydrase enhances the uptake rate of CO 2 into an absorption liquid Algae regenerate the carbonatebased absorption liquid Carbonic Anhydrase II Amine based CO 2 capture Cultivation of algae directly on CO 2 captured in amine-based solvents Algae regenerate solvent which can be reused for CO 2 capture Spirulina platensis 21/06/2012 (source: Premkumar et al. (2005) PNAS, 102 (21) p, ) (source olio_da_alghe.html) 30

31 Route 1: Enzyme promoted CO 2 capture Carbonate solutions are cheap compared to other CO 2 absorption liquids, but have a slow CO 2 uptake rate Addition of carbonic anhydrase to sodium carbonate solution increases the rate of CO 2 uptake Carbonic Anhydrase effects on CO 2 loading 21/06/2012 Kinetic experiments showing the rate of CO 2 loading in the reference (, 2M sodium carbonate) and catalyzed (, 2M sodium carbonate plus 400mg/L carbonic anhydrase) tests 31

32 Route 1: Enzyme promoted CO 2 capture Concept process design of a carbonate based CO 2 capture system using carbonic anhydrase as promoter and algae as solvent regenerator 21/06/

33 Route 2: Combining CO 2 capture with amine based solvents & algae cultivation The uptake of CO 2 by a amine-based solvent CO 2 stripping of solvent by consumption through algae in a solvent & medium solution Recycle of the solvent for new cycle of CO 2 uptake The algae biomass can be used for product. 21/06/

34 Absorber Route 2: Algae-mediated CO 2 desorption from amine-based solvents Makeup water CO 2 -lean gas Concept process design of a amine based CO C o n c e p t 2 capture system using algae as solvent regenerator Top Tray Lean solvent Products Light Algae Bioreactor CO 2 -rich gas Bottom Tray Algae Biomass Nutrients Biomass Down stream processing Rich solvent 21/06/

35 Capture solvent selection criteria 1. Non-toxic to algae culture 2. Slow biodegradable by algae culture 3. Cheap/abundant 4. Efficient capture of CO2 (partly absorbed CO2 should be bicarbonate species) It is of importance to note that 90% CO2 capture is not the objective 21/06/

36 From problem to business /06/

37 Acknowledgement Some references US (A1) - ENZYME PROMOTED CO2 CAPTURE INTEGRATED WITH ALGAE PRODUCTION Goetheer et al. WO (A1) - COMBINING ALGAE CULTIVATION AND CO2 CAPTURE Goetheer et al. 21/06/