1

Pressurized Chemical Looping Combustion for Zero Emissions Heavy Oil Extraction

6th High Temperature Solid Looping Cycles Network Meeting

Milan, Italy

September 1st, 2015

Dennis Lu, Philippe Navarri, Omid Ashrafi, Scott Champagne,

Robert Symonds and Robin Hughes

CanmetENERGY

2

Background

Produce hydrogen, steam

and power for 20 - 30

kbpd SAGD facilities

SAGD - steam assisted

gravity drainage

Partial upgrading

Natural gas as fuel

Other high hydrogen fuels

as the technology advances

CO2 capture

Minimize capital cost

3

Current Target Market

Purchased and

produced gas for in situ

oil recovery

• A market of about 60

million m3/d of fuel gas

by 2022 in Alberta

• Equivalent to 42 Mt

CO2 or 6% of predicted

emissions for the

nation

• Ultra heavy oil in other

regions internationally

Purchased and

produced gas for mining

and upgrading

• A market of about 30

million m3/d of fuel

gas by 2022 in

Alberta

Hydrogen, Steam and Power Production

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Christina Lake SAGD

The site of Cenovus’ planned

chemical looping pilot plant (10 MWth)

to generate steam (CLC steam

generator) using Ni-based oxygen

carriers with natural gas for

enhanced bitumen recovery (Sit et al.

2012).

Christina Lake SAGD central

processing facility near Fort McMurray,

Alberta, Canada

Annual production for 2014 averaged

71,186 bpd, an increase of 102% over

2013 volumes of 35,317 bpd, marking

the company’s seventh consecutive

year of annual production gains.

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Outline

Process Description

PCLC for Steam Generation

PCLC Kinetic Study

Pinch Analysis

Integrated Process Simulation

Conclusions

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Christina Lake SAGD Process

7

Process heat exchanger

11-E-501 15.6

187.9 176.6 50 43,245 15.6 Glycol cooler

916,727 1,520 18,810

130.0 130.0 Glycol heater

187.9 134.0 133.6 130.0 50.0

915,207 258,680 Temperature °C

11-E-103 11-E-106 11-E-114A/B Flow rate kg/h

130.0 85.0 85.0 85.0

114,126 711,493

11-E-130A/C 11-E-555

50 5

130.0 114.4 85.0 85.0 19,947 200

586,327 20,140

11-E-125 11-E-128 81.6 94.0

11-E-125 743,437 105.0

299.8 Diluted Acid 50 90.3

738,441

200.0 300.0 85.1 105.1

20,140 923,097 208.0 704,378

200.0

26,616 200.0

300.0

184,655 172.0 160.4 155.1 103.9 105.1

90.0 165.1 200.0 923,097

137,800 11-E-413 11-E-410 11-E-103

11-E-433 11-E-410 -0.2 64

40,313

199.7 199.0 105.0

26,616

11-E-461 11-E-463

90.2

125,398

90.2 65.0

12,402

11-E-450

11-E-330

Oil Removal

Skim Tank

De-OiledWater Tank

FWKOInlet Separator

Tretaers

Brackishwater

Hot LimeSoftener

(HLS)Afterfilter +WAC package

Dilbit

MP Steam

HP Steam to wells

MP SteamSeparator

Steam Generator (6 OTSGs in parallel)

HP SteamSeparator

EvaporatorFeed Tank

EvaporatorPackage

Distillate

Evaporator Blowdown to Disposal Water Tank

Produced WaterProduced Water

Dilbit

Produced Emulsion

Produced Gas

Glycol

Air

Fuel Gas

Diluent

Sales Oil

Diluent

To 11-E-413

To HLS

MP Steam

BFWTank

Lime, MgO, Soda ash

BFW

Simplified Process Flow Diagram

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Project Objective

Process integration and constraints drive PCLC reactor design and

conditions

Pinch analysis of existing SAGD facility is performed to design an energy efficient

process with maximum heat recovery

Reactor configuration and operating pressure are set by dimensional constraints

Philosophy - operate at minimum pressure that satisfies constraints

considering firing rate, reaction rate, and heat transfer

Case 1: Natural gas firing, nickel oxygen carrier, atmospheric pressure;

Case 2: Natural gas firing, ilmenite oxygen carrier, atmospheric pressure;

Case 3: Natural gas firing, ilmenite oxygen carrier, 8 bar (g) pressure;

Case 4: Natural gas firing, ilmenite oxygen carrier, 15 bar (g) pressure;

Case 5: Case 4: Natural gas firing, ilmenite oxygen carrier, 23 bar (g) pressure;

Case 6: Natural gas firing, ilmenite oxygen carrier, 15 bar (g) pressure, duct firing for

partial CO2 capture;

Case 7: Natural gas firing, ilmenite oxygen carrier, 15 bar(g) pressure, hydrogen

production for partial upgrading;

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Advantages of Pressurized CLC

Increasing pressure will increase power generation by the gas turbine increasing overall system efficiency

High pressure CO2 can be obtained from FR outlet reducing parasitic power losses for CO2 compression to pipeline conditions

Increased system pressure permits recovery of latent heat of water vaporization at temperatures suitable for integration with steam cycle

Pressurized fluid beds provide improved reactant mixing

With the increase of pressure, the steam concentration increases thereby increasing the reaction rate of fuel gasification

Fuel conversion in a pressurized fluidized bed PFBC is an established technology – data and know how can be transferred to P-CLC to reduce development risk and time

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Pressurized CLC Technology in the Canadian Energy Context

Very high efficiency 40 to 47% HHV for 96% CO2 capture and cost of power

with CCS reduced by 25% based on Worley Parsons techno-economic analysis

Reduce oil sands emissions and increase productivity

Suitable for current and

potential future NOX, SOX,

and CO2 regulations

Develop major export

market for Canadian mining

sector for green technology

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Areas for PCLC Kinetic Study

Oxygen carrier development

Naturally occurring materials: ilmenite, iron ore, etc.

Low cost and environmental benign

Challenges: reactivity, attrition, fouling and agglomeration

Bench-scale studies: pressurized TGA, fixed bed and small bubbling bed

Pilot-scale investigation: engineering, construction and operation

Fuel reactivity

Gaseous fuel: natural gas, syngas, fuel gas, shale gas

Liquid fuels: bitumen, asphaltene

Solid fuels: coal, pet coke, biomass

Provide detailed assessment of the benefits of CLC via process configuration and simulation

Process modeling and simulation

Use experimental data from pilot plant data to validate models

Performance, emissions and economic

Solids characterization

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O2 Carrier: Ilmenites, hematite

Particle size: 45 – 300 m

Sample weight: 40, 80 mg

Gas Fuel: CO, CH4

Temperature: 850, 950, 1050°C

Total Pressure: up to 50 bar

Partial PCO: 3.2 – 15.3 bar

Partial PO2 : 0.9 – 3.2 bar

Reaction Kinetics Study on PCLC

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Effect of Pressure

(c) Effect of the total pressure(b) Effect of CH4 partial pressure

0

0.2

0.4

0.6

0.8

1

0 5 10 15 20 25 30

Co

nv

ers

ion

Relative time (min)

0 MPa 0.3

0.6

-4

-3

-2

-1

0

0 5 10 15 20 25 30

Re

lati

ve

ma

ss c

ha

ng

e (

%)

Relative time (min)

0 MPa

0.3

0.6

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Effect of Temperature

(b) at high pressure

(a) at low pressure

(c) Effect of steam at low pressure

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Fe-Ti-O2 Phase Diagram

FactSage, T=950°C, P=16 bar

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CLC Profiles

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Effect of Pressure & Temp.(in oxidized state)

8 bar 16 bar

24 bar 51 bar

850oC

950oC

1050oC

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20 cycles

4 cycles

1 23

Fe Ti

Pre-oxidized (Cross section)

Spectrum Ti Fe

#1 45.15 19.51

#2 26.92 37.38

#3 10.12 60.01

4 cycles, T=950 oC, Pt=8 bar, pCO=4.8 bar

1

2

4

3

5

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Spectrum Ti Fe

# 1 4.94 86.55

# 2 3.15 92.15

# 3 14.98 60.90

# 4 6.47 87.17

# 5 16.00 56.55

# 6 22.44 48.47

SEM & EDX

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Kinetic Modelling

• A grain model with changing grain size with chemical

reaction control is applied to the redox reactions of

ilmenite at elevated pressure, 𝑡

𝜏= 1 − (1 − X) 1 3

• where τ is the time for reaching the total conversion, τ =𝜌𝑚𝑟𝑔 𝑏𝑘𝑠𝑃𝐺

𝑛

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Process heat exchanger

11-E-501 15.6

187.9 176.6 50 43,245 15.6 Glycol cooler

916,727 1,520 18,810

130.0 130.0 Glycol heater

187.9 134.0 133.6 130.0 50.0

915,207 258,680 Temperature °C

11-E-103 11-E-106 11-E-114A/B Flow rate kg/h

130.0 85.0 85.0 85.0

114,126 711,493

11-E-130A/C 11-E-555

50 5

130.0 114.4 85.0 85.0 19,947 200

586,327 20,140

11-E-125 11-E-128 81.6 94.0

11-E-125 743,437 105.0

299.8 Diluted Acid 50 90.3

738,441

200.0 300.0 85.1 105.1

20,140 923,097 208.0 704,378

200.0

26,616 200.0

300.0

184,655 172.0 160.4 155.1 103.9 105.1

90.0 165.1 200.0 923,097

137,800 11-E-413 11-E-410 11-E-103

11-E-433 11-E-410 -0.2 64

40,313

199.7 199.0 105.0

26,616

11-E-461 11-E-463

90.2

125,398

90.2 65.0

12,402

11-E-450

11-E-330

Oil Removal

Skim Tank

De-OiledWater Tank

FWKOInlet Separator

Tretaers

Brackishwater

Hot LimeSoftener

(HLS)Afterfilter +WAC package

Dilbit

MP Steam

HP Steam to wells

MP SteamSeparator

Steam Generator (6 OTSGs in parallel)

HP SteamSeparator

EvaporatorFeed Tank

EvaporatorPackage

Distillate

Evaporator Blowdown to Disposal Water Tank

Produced WaterProduced Water

Dilbit

Produced Emulsion

Produced Gas

Glycol

Air

Fuel Gas

Diluent

Sales Oil

Diluent

To 11-E-413

To HLS

MP Steam

BFWTank

Lime, MgO, Soda ash

BFW

Pinch Analysis

Stream NameInitial

Temperature (°C)

Final

Temperature (°C)Heat load (kW)

Produced emulsion from V-101 187.9 132.1 57,968

Produced water (V-110) 130.0 85.0 32,373

Produced water (V-112) 130.0 85.0 6,308

Dilbit 130.0 50.0 11,644

Steam to BFW tank 200.0 105.0 17,432

Blowdown 200.0 90.0 18,210

Evaporator blowdown 90.2 65.0 365

Dilution water 90.3 50.0 1,153

Produced gas 176.6 50.0 692

Boiler feedwater 103.9 300.0 234,662

De-oiled water 81.3 105.0 21,305

Fuel gas -0.2 64.0 1,936

Brackish water 5.0 50.0 1,077

Flue gas 221.0 130.0 19,782

Steam to HLS 200.0 105.0 9,982

Diluent 15.6 80.0 1,452

Combustion air 0.0 175.0 34,998

Data extraction Simplified Process Flow Diagram

Scope for energy savings

Heat exchanges creating

inefficiencies

Base Case Heat

Exchanger Network

Composite Curves

Improved Heat Exchanger Network

Changes that Increase Heat Recovery

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Process Design Conditions

Design conditions

Oil production capacity: 30,000 bbl/d

Steam to Oil Ratio (SOR): 3.5

Gas to Oil Ratio (GOR): 5

Reservoir water retention: 5%

Energy and water conservation aspects

Process-process heat recovery

Large glycol system used to recover heat from some process streams

and to preheat other streams

Steam produced in OTSGs, no cogeneration plant

HP blowdown from OTSGs depressurized and flashed MP steam fully

recovered (energy and water conservation)

Saline water (called brackish water) used as make-up water

Blowdown treated in MVR evaporator and distillate recycled

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Pinch Analysis: Composite Curves

A graphical representation of the process heating and cooling requirements

Assuming maximum heat recovery:

Minimum hot and cold utility consumptions, potential for energy savings can be calculated

Heat exchanges creating inefficiencies can be identified

Pinch point

Minimum temperature

approach: DTmin = 10°C

Pinch point: 195°C

Potential for energy savings

~ 50 MW

Of this potential, ~ 6.6 MW

from the OTSGs flue gas

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Pinch Analysis: Identification of Heat

Exchanges Creating Inefficiencies

Identify heat exchanges that

transfer heat across the pinch

BFW heating

Steam injection in HLS

Flue gas rejected to environment

Hypothesis for retrofit

Flue gas heat recovery limited to

energy above 130°C (acid dew

point) to avoid condensation

BFW final temperature is at the

evaporation temperature under

OTSGs operating pressure to allow

further preheating

Diluent can be preheated before

mixing to save some energy

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Pinch Analysis: Before and After Retrofit

The BlackPearl Blackrod project is a recent SAGD plant designed using well

established technologies for energy and water conservation

However, a pinch analysis of the process revealed that significant energy

savings can be achieved by improving heat recovery without affecting the

water consumption

Opportunities for improving the current heat recovery system include:

Relocate 1 heat exchanger in the BFW preheat train

Increase surface area of existing process heat exchangers

Further preheat the BFW using Dilbit, MP steam in Lime Softener and Flue Gas

Preheat the Combustion Air using Produced Water and Flue Gas

Use extra energy in Dilbit to preheat the Diluent and the Brackish Water

Overall, the improved heat recovery system would:

Reduce hot utility requirement by approximately ~ 41 MW

Reduce the amount of glycol circulating throughout the plant therefore simplifying

the design as fewer heat exchangers and smaller pumps would be needed

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Simulation of PCLC (UniSim)

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Simulation of PCLC (UniSim)

(a) Feed Preparation (b) Fuel Reactor

(c) Air Reactor (d) Air Reactor Gas Turbine

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PCLC Process Conditions

Process conditions

SAGD project EIA 30000 BPCD case study (BlackPearl, 2012).

HP: 299.2°C at 8.57 MPa (80% quality).

BFW: 103.1°C at 1.5 MPa

Key process assumptions

Input for system is 75 MWth (natural gas).

Pump adiabatic efficiency is 80.0%.

Compressor polytropic efficiency is 86.75% (@ Compression ratio=2.5).

Shell and tube heat exchangers are represented by heaters and coolers in

simulation, where “heaters” and “coolers” are used in the simulation pressure drop is

20 kPa (2%) on the gas side, 40 kPa (4%) on the liquid side.

Oxygen carrier purge stream is 15% of looped carrier following fuel reactor.

The Peng Robinson fluid package is used for the simulation.

Pressurization unit operations for solids are modeled as single outlet vessels with

negligible pressure drop.

Exit temperature at inter-stage cooling is 35oC. Maximum operation temperature for

fine filtration is 400oC.

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Simulation Summary

Data Type Value

Auxiliary Power Demand, kWe

Air Compressor

CO2 processing Unit

Produced Gas Compressors

Boiler Feed Water Pumps

AR Water Pump

FR Water Pump

TOTAL AUXILIARIES, kWe

12,739

509.19

30.01

342.8

1.222

0

13,622.22

Net Plant Efficiency, %

Net Plant Heat Rate, Btu/kWh

CO2 Product, kg/h 13,580

H2 Product, kg/h 249.3

Emissions, g/MJ

SO2

NOx

Particulate Matter

Stream/Data Type Value

Natural Gas Input

Flow Rate (kg/h)

Pressure (kPa)

Temperature (°C)

5692

7094

-0.2

Boiler Feed Water

Flow Rate (kg/h)

Pressure (kPa)

Temperature (°C)

102600

190.1

103.0

Compressor Air Input

Flow Rate (kg/h)

Pressure (kPa)

Temperature (°C)

129500

91.10

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Produced Gas Input 1

Flow Rate (kg/h)

Pressure (kPa)

Temperature (°C)

96.73

464.1

49.80

Produced Gas Input 2

Flow Rate (kg/h)

Pressure (kPa)

Temperature (°C)

372.1

369.1

65.30

O2 Carrier Inventory in FR flow rate (kg/h) 1,333,000

O2 Carrier Inventory in AR flow rate (kg/h) 1,116,000

O2 Carrier Make Up flow rate (kg/h) 191,600

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Integrated PCLC in SAGD Process

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PCLC has been confirmed to be an excellent candidate for steam production

at SAGD facilities using natural gas as fuel to meet current business needs of

the Canadian Oil Sands industries.

Integration of PCLC technology into a SAGD process can result in a system

design that permits more optimal operations with the SAGD central

processing facility by increasing heat recovery.

Process configurations for the integration of PCLC and SAGD have been

created to help researchers at CanmetENERGY further conduct process

simulations and heat integration analyses.

Canadian ilmenite is very well suited to pressurized chemical looping

combustion applications, plus its low cost and minimal environmental impact.

CanmetENERGY plans to develop PCLC for production of H2, steam and

power using a naturally occurring oxygen carrier from TRL 2 to TRL 4

resulting in a small pilot scale (~200 kWth) demonstration.

Conclusion

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This research project was sponsored and funded by the PERD

(Program for Energy Research and Development) program of

Natural Resources Canada, Government of Canada.

Ilmenite samples were kindly supplied by Rio Tinto Iron & Titanium.

Acknowledgment