Theme A Overview: Recovery, Processing and Capture John Grace Clean Energy Research Centre University of British Columbia Vancouver CMC Annual Conference, Banff, May 2014
Theme A Overview: Recovery, Processing and Capture
John Grace Clean Energy Research Centre University of British Columbia
Vancouver
CMC Annual Conference,
Banff, May 2014
Criteria in Choosing Projects • Potential to be game-changing • Potential to harness excellent Canadian
researchers, working together in teams • Relevance to long-term Canadian needs. • Linkages, or potential linkages, with Canadian
industry. • Potential to train high-quality HQP.
Theme A, Round 1 Projects • Integrated gasification with looping CO2 capture
(Ellis, Kaliaguine, deLasa, Mahinpey, Macchi et al.) – A01
• Fluidized bed gasification of low-grade coals and petcoke (Hills, Pugsley, Chaouki, Gupta et al.) – A02
• Rapid routes to carbon-efficient recovery of bitumen and heavy oil (Gates, Larter) – A03
• Development of direct air capture technology
(Keith, Grace, Lim, Anthony, Macchi) - A04
• Hydrogen production from waste asphaltenes (Pereira Almao) – A05.
A1: Integrated Fluidized Bed Gasification with Looping CO2 Capture
(UBC, UCalgary, Laval, Western, UOttawa, CANMET)
4
Gasifier Calciner
Fuel
Sorbent with CO2
Sorbent
Concentrated CO2
H2O
Syngas
Overall Goal: • To develop and characterize poten2al CO2 capture sorbents • To test most promising sorbents in pilot plant for gasifica2on and CO2 capture
Sorbents synthesized, prepared, pelle2zed, coated and/or tested: • Limestone (crushed/pelle2zed) • Lithium orthosilicate • Core-‐shell limestone pellets
Limestone vs synthe2c sorbents CO2 capture efficiency
Limestone and its pellets: Ace2fica2on and Al(OH)3 binder promo2ng higher CO2 capture capacity
Prepared coa2ng of shells of mesostructured SiO2, TiO2, ZrO2 and SiO2-‐ZrO2, CaCO3 or Cadomin par2cles
Chemical looping unit: Operatability tested using limestone or pellets
ALri2on tes2ng of sorbents
Fuel/Chemical
Fuel cell
Transport fuel
Oil upgrading
Combustor
Coal
Petcoke
Biomass
Waste
BFBGasifier
Cal
cina
tor
Gas TurbineCompressor
Steam Turbine
HRSG
PSAH2S / NH3
removal
Generator
Generator
Electric Power
Electric Power
Electric Power
Condenser
Condenser
Condenser
SLC
Condenser
ASU
CO2 Sequestration
RecycledWater
RecycledWater
RecycledWater
RecycledWater
Air
N2 to Combustion
O2
PSAOff-Gas
Waste
Off-Gas to Calciner
Clean Syngas
H2
RecycledParticulates
SteamCaCO3
CaO
CO2,H2O
Syngas
H2
CO2
N2
H2O,N2
Air
Steam Water
O2,H2O,N2
WGS
Model IGCC with in-‐situ CO2 capture using lime (CaO) using ASPEN Plus
Gasifier: 750˚C, 32 barg CaO-‐Carbon (CaO:C) molar Ra2o: 1.5:1 Calciner: 900˚C, 0 barg
A1
Benefication &
Catalyst Addition
UofA
Gasifica=on Kine=cs UofT: Drop in Gasifier
UCalgary: TGA Poly: Fluidized TGA
Fluidized Bed Studies EP: 20 cm dia, Atm P,
< 1000°C (Poly)
Hot gas Clean-up UCalgary
Coal Ash-‐free or Low ash
Gas Comp
CO, H2, CH4, CO2
Chemical Looping CO2 (A1)
Modeling UofS: CFD of fluidiza2on
UCalgary, Poly: Process Economics
Overall Goal: • To develop a fluidized bed cataly2c gasifica2on process that improves gasifica2on efficiency and produces a capture-‐ready stream of CO2.
A2: Fluidized Bed Catalytic Gasification of Low-Grade Coals
(UCalgary, UofS, École Poly, UofA, UofT)
Proximate analysis (wt%, db) Ultimate analysis (wt%, daf)
VM FC Ash VM/FC C H N S O*
GEN-raw 31.5 38.3 30.5 0.8 73.1 4.3 1.0 0.4 21.2
GEN-AF 69.5 30.5 682 ppm# 2.3 87.2 5.3 3.4 0.1 4.3
GEN-res 17.3 24.8 57.9 0.7 76.0 5.0 2.1 1.2 15.7
GEN-AF char 0.0 100.0 0.0 - 90.9 2.5 1.8 0.1 4.7
GEN-LAP 33.6 58.3 8.15 0.58 69.7 4.8 1.0 0.4 24.1
VM = volatile matter, FC = fixed carbon, db = dry basis, daf = dry and ash free, *Oxygen content by difference, #determined by ICP-MS
Properties of Genesee coal samples (raw, ash free, residue, char, and low-ash)
Ca(OH)2 decomposition: Comparison between Conventional and Fluidized Bed TGAs
grams!
Coupling Aspen Plus flowsheet with external Fortran files
Drop-down Micro Reactor for Gasification studies with Steam Reaction scheme:
K2CO3 on ash-free coal heated in N2 or CO2 atmosphere.
A03 -‐ Rapid Routes to Carbon-‐Efficient Recovery of Bitumen and Heavy Oil -‐ Gates and Larter (UCalgary)
OBJECTIVES: 1. Analyse major CO2 emission sources from exis2ng thermal bitumen recovery
methods OUTCOMES: Full analysis of CO2 emissions from SAGD well pairs versus resource (including effect of reservoir geology)
2. Reduce Emissions to Atmosphere: Routes to reduce carbon in exis2ng processes: a. BeLer well design or placement to reduce carbon intensity
OUTCOMES: Up to 25% reduc=on in Steam-‐Oil and CO2-‐Oil Ra=o b. Op2miza2on of opera2ng strategies to reduce carbon intensity
OUTCOMES: Up to 30% reduc=on in Steam-‐Oil and CO2-‐Oil Ra=os c. Mul2-‐well control methods for robust recovery process design e.g.
smart pads OUTCOMES: Up to 25% reduc=on in Steam-‐Oil and CO2-‐Oil Ra=os
d. Reservoir s2mula2on technologies to improve oil quality to reduce carbon intensity of a recovery process, e.g. reservoir precondi2oning by injec2on of agents in mobile water OUTCOMES: Up to 20% reduc=on in Steam-‐Oil and CO2-‐Oil Ra=os
A03 – Gates & Larter (con=nued)
3. Zero Emission to Atmosphere Processes: Evaluate routes to zero or neutral carbon emission:
a. Integrated recovery process design and CO2 sequestra2on e.g. shallow water aquifers, SAGD chambers OUTCOMES: Possible, but according to industry, CO2 sequestra=on in shallow water aquifers e.g. Grand Rapids Forma=on, directly under SAGD opera=ons, presents a large risk with respect to CO2 leakage Results suggest that if dissolu=on and mineraliza=on occur in shallow water zone, to store 1 MT/yr for 30 years, need 98 km2 of 75 m thick aquifer.
b. Novel steam genera2on e.g. steam-‐methane reforming with conversion of CO2 to carbon phases
OUTCOMES: Direct contact steam genera=on – 1 patent filed for SAGD opera=ons (not directly funded by CMC) Decarbonizer for Oil Sands Opera=on – decomposes natural gas to carbon black and hydrogen, and then burns hydrogen as fuel.
Lowig/Direct Alkali Regenera2on System processes can be adapted for regenera2on of NaOH for use in cyclic CO2 air capture
Regenera2on involves CO2 release from solid-‐state reac2on of Na2CO3 and Fe2O3, followed by hydrolysis of NaFeO2 to recover NaOH
A04 – Direct Air Capture Technology (UCalgary, UBC, UOttawa, Canmet)
Objective: Seek ways of viably removing CO2 from ambient air in a cyclic manner.
Ball milling the Fe2O3 Na2CO3 mixture for 30
min reduces the temperature of the
CO2 releasing reac2on by 200-‐300°C and
increasing conversion for similar 2me period
Contrac2ng cylinder surface reac2on
Diffusion limited kine2cs with sharp increase in rate at Na2CO3 mel2ng point
Leaching of the NaFeO2 product can be carried out at lower temperature for reduced par2cle size.
A04 - CO2 Capture from Ambient Air via Lime-Based Sorbents UOttawa, Canmet-Ottawa
Objective: Investigate performance of a pelletized lime-based sorbent for CO2 capture from ambient air over 5 carbonation/calcination cycles.
Method: Fixed bed calcination occurred at simulated oxy-fuel conditions in 100% CO2 at 920°C for 12 min. Lime sorbent contained 10 wt % calcium aluminate cement to improve its initial sorption properties via formation of mayenite.
Result 1) Humidifying the air (e.g., above 40% R.H.) and pre-hydrating the sorbent are crucial for rapid CO2 uptake and elevated conversion. Carbonation occurs in nano-sized water droplets at sorbent surface where the ions of dissolved of CO2 and Ca(OH)2 react. Result 2) The pelletized lime-based sorbent capacity decays with each regeneration cycle (~30% after 5 cycles). Note: Natural lime particles fared similarly.
Achievement/Path Forward: Hydrated lime can efficiently capture CO2 from moist air, but sorbent regeneration is an important problem. More cycles will identify if there is an acceptable asymptotic lower conversion limit while attempting to better protect the sorbent (e.g., reduce the calcination period).
A05: Hydrogen Production and Waste Processing
Principal Investigator: Pedro Pereira-Almao HQP: Azfar Hassan, Nashaat N. Nassar, Francisco Lopez-
Linares Graduate Student: Lante Carbognani-Arambarri
Intern: German Luna
University of Calgary, AB, Canada
Vacuum Residue
Adsorption of Asphaltenes in
a (Fixed Bed Reactor)
H2O(g)
CSG of adsorbed
asphaltenes
Partially Deasphalte
d VR
TC/SCC
Visbroken Vac Residue
Catalytic steam gasification combined with dry reforming of methane would lead to 50% reduction in CO2
Project Objec2ves A. Prepare macroporous-‐mesoporous kaolin-‐based cataly2c material suitable for asphaltenes adsorp2on. B. Fundamental study of asphaltene adsorp2on over transi2on metal oxide nanopar2cles and other materials. C. Visbroken feed prepara2on close to instability, so they can readily adsorb. D. Study effect of thermal cracking of feed on its adsorp2on. E. Bench scale fixed bed reactor set-‐up for adsorp2on and gasifica2on. F. Post adsorp2on cataly2c steam gasifica2on of adsorbed waste material in fixed bed reactor.
A05
Overall Achievements New Process Scheme
Adsorp2on Experiments
Thirteen journal publica2ons so far. Several presenta2ons in na2onal and interna2onal conferences. Catalyst prepared needs to be tested for cataly2c steam cracking (CSC) and cataly2c steam gasifica2on (CSG) at pilot plant scale.
Nanopar2cles adsorbed asphaltenes
Thermal cracking improved uptake by the catalyst
Thermal cracking
Visbroken Residue
A05
A5
Theme A, Rounds 2 & 3 Projects • Easy-Release CO2 Capture Sorbents at the
Molecular Level (Shimizu, Woo) – A221
• High Performance Amine-Impregnated Solid Sorbents for Post-Combustion CO2 Capture (Gupta et al.) – A239
• Material Development and Optimization for Zero CO2 Emission Energy Production (Sayari, Birss, Thangadurai) – A211
• CO2-microbubbles for increased sequestration & EOR potential in oil/gas reservoirs (Trivedi et al.) - A238
• CaO/CuO Sorbent for Post-Combustion CO2 Capture (Macchi, Mehrani, Anthony, Legros, Patience) – A346
A221-Designing Easy Release CO2 Sorbents Shimizu (UCalgary) and Woo (UOttawa)
General Goal: Develop better solid CO2 sorbents through combined computer modelling and synthesis of new crystalline porous solids.
Specific Goals: - Explore new types of porous solids, called metal organic frameworks (MOFs), and develop systems with not only good CO2 capacity, but also improved stability to water. - Develop a means of computationally screening new MOFs and simulating their CO2 uptake in high throughput method.
A221-Designing Easy Release CO2 Sorbents Main Outcomes: - Two new approaches to water-stable MOFs were generated, and new approaches to raising heat of adsorption for CO2 were studied. - Patent filed for a new solid sorbent (CALF-20) that is steam stable, has excellent capacity at flue gas CO2 pressures and has a scalable preparation. - Collaboration struck to carry out nanostructuring of CALF-20 to improve heat flow and kinetics of gas permeability. - New algorithm developed to rapidly generate and screen new MOFs for CO2 capacity. - Predictions have been made for new solid sorbents that would be world record materials for capacity.
A 239 High-Performance Amine-Impregnated Solid Sorbents for Post Combustion CO2 Capture &
Techno-Economic Assessment R. Gupta, S. Kuznicki, W. Chen, Z. Hashisho (UAlberta)
+ P. Sarkar (Alberta Innovates - Technology Futures)
Goals: - Synthesize and characterize amine-functionalized supported sorbents (meso-porous silica, zeolites, activated petcoke and CNT).
- Determine adsorption/desorption kinetics.
- Find effects of flue gas moisture, O2, Sox & NOx on multiple-cycle tests with N2 or steam regeneration in TGA and bench-scale packed bed.
- Test selected sorbents on slip stream from coal-fired power plant.
- Techno-economic assessment of CO2 capture with novel sorbents.
A239 - Achievements • Successfulluy synthesized amine-functionalized solid
sorbents (meso-porous, silica, zeolites, activated petcoke and CNT) by impregnation and grafting with 30-60% amine loadings.
• Maximum single cycle adsorption capacity of 4 mmol/g sorbent (16.5% by wt) for most sorbents.
• Desorption step was very slow, but steam desorption was very fast.
• Moisture facilitated adsorption, but 4% O2 decreased adsorption capacity. SOx & NOx studies not completed.
• ASPEN techno-economic assessment and slip stream studies continuing.
500 oC
COMBINED SOFC-SOEC WITH INTEGRATED CO2 CAPTURE/STORAGE
• Develop combined SOFC-‐SOEC with capture and separa2on of pure CO2. • Storage, sequestra2on and/or recycling of CO2 as feed for SOEC
SELECTIVE ADSORPTION OF SO2 Materials used for SO2 Sensor: TiO2+SnO2 mixed composites
CO2 Sensor: Ba2Ca0.66Nb0.68Fe0.66O6-‐δ
SO2 in N2 CO2 in Air PPM LEVEL DETECTION OF SO2 AND CO2 BEFORE AND AFTER CO2 CAPTURE
CO2 adsorbents • Grafted triamine and impregnated polyethylenimine on pore-expanded MCM-41 exhibits high CO2 adsorption capacity, high selectivity and fast adsorption-desorption kinetics. • Moisture enhances CO2 adsorption and prevents deactivation of amine adsorbents via formation of urea linkages. • Materials are stable in simulated SOFC exhaust gas (humid 42% H2; 7% CO, balance CO2) Selective SO2 adsorbents protective filter for CO2 adsorbents) • Grafted N,N-dimethylpropylamine and impregnated tertiary amine-containing PEI and polypropylamine dendrimers impregnated PE-MCM-41 exhibited excellent reversible adsorption of SO2 with very high selectivity in the presence of CO2. • No deactivation in high concentration of dry or humid CO2. • Moisture enhanced SO2 uptake on all new adsorbents. Novel materials for reversible SOFC-SOEC • Developed LSFCr/GDC/YSZ/GDC/LSFCr symmetrical SOFC/SOEC. • GDC buffer layer used to prevent interphase reactions. • In SOFC mode, fuel is converted to CO2 and steam; in SOEC mode, H2 + CO syngas formed. Novel SO2 sensors • Semiconducting TiO2:SnO2 composite (3:1 molar ratio) was synthesized by sintering pellets at 700oC in air and tested for the detection of ppm levels of SO2. • Excellent reproducible sensitivity for SO2 in N2 at 400oC, with 90% of sensing time (t90) of ~5 min. • Linear relation between ppm level of SO2 and sensitivity. • Material stable up to 3000 ppm SO2 in air at 700oC. • Perovskite-type Fe-doped barium calcium niobate (BCN) is also a potential resistive-type sensor to estimate efficiency of CO2 capture capacity of adsorbents.
A238 - CO2 Microbubbles for Improved Sequestration and EOR
J. Trivedi, E. Kuru, P. Choi (UAlberta) and M. Dong (UCalgary) Objectives: Replace traditional CO2 injection into oil and gas reservoirs by alternative safe and secure method. Improve oil/gas recovery.
Underlying Idea: Inject CO2 / Flue gas as microbubbles for storage in oil/gas reservoirs. Research to understand stability and applications of microbubbles for underground storage.
Achievements • Studied mixing method, type of surfactant and polymer, and their
op2mal concentra2ons for genera2ng stable CO2 microbubbles using rheological characteriza2on, microscopic study and PVT analysis.
• Studied effect of oil type (light and heavy) on destabiliza2on of CO2 microbubbles. Correlated bulk foam test results with porous media experiments.
• Conducted CO2 microbubble flooding into oil saturated core and linear visual sandpack to understand CO2 microbubble flow through porous media and oil recovery.
Result Highlights • CO2 microbubbles generated in-‐situ (inside porous media) have beLer
stability, and performance for CO2 storage, as well as oil recovery, compared to conven2onal CO2 gas injec2on, foam injec2on, and ex-‐situ generated microbubble injec2on.
• Oil recovery could be increased by 15-‐17% with less CO2 produc2on/recycling.
A346: Pre- and Post-Combustion CO2 Capture using Composite CaO/CuO Sorbents: UOttawa, Ecole Polytechnique, UCalgary and Canmet
26
Pre-‐combus=on CO2 capture
Objec=ve: Inves2gate various sorbent formula2ons and their sustained CO2 capture capacity (conversion and aLri2on resistance) over mul2ples cycles in realis2c gaseous environments and gas-‐solid contac2ng paLerns. Combined with reactor modeling and process simula2on, this could provide process technico-‐economic proof-‐of-‐concept.
Post-‐combus=on CO2 capture Solids Recycle Loop
A346 Post-Combustion Process – Initial results: Although recirculating solids from air reactor to calciner
reduces fuel (CH4) requirement, it increases solids circulation rate.
CaO/CuO pellets have similar attrition behaviour as FCC and VPO catalysts in circulating fluidized bed processes.
Material and energy balances suggest marginal T-gradient during calcination.
Pre-Combustion (Gasification) Process – Initial results: Cu/CaO pellets must enter gasifier. (Otherwise CuO would be
reduced.) Cu will be difficult to oxidize due to CaCO3 layer. Thus some calcination in air reactor or separate CaO and Cu
pellets are likely to be only ways forward.
Some Overall Observations: Theme A • Very limited industry involvement and funding. • Some good academic work accomplished leading to
journal papers, presentations + some patents. • Work is continuing in most projects beyond the end
of the CMC funding. • Nature makes it difficult to achieve breakthroughs. • Some “real” collaboration within projects. Some
linkages where there were none previously. • Virtually no cross-over within Theme A or with the
other three themes. • Some excellent HQP training: core of trained and
committed young people are the hope for the future.