Technologies For Carbon Capture in Oil Refineries: Ivano Miracca Saipem S.P.A

Technologies for Carbon Capture in Oil Refineries
Ivano Miracca Saipem s.p.a.

WEC Italia Cattura e Stoccaggio della CO2 (CCS) Roma, October 18, 2011
Saipem Highlights Leading Global EP(I)C General Contractor

2010 Revenues End-of-2010 Backlog 11.2 B 20.5 B
40,000 employees, of which 7,000 Engineers & Project Managers Operating in more than 70 countries, more than 50 permanent establishments, employees from 122 nationalities Key local employer and investor in strategic markets
Full service EP(I)C provider

Distinctive frontier focus in Oil & Gas industries Most modern, technologically advanced offshore construction fleet Designed and built:
Over 90 grass roots complexes, 1,700 process units
Over 120,000 km of land pipelines, sealines and trunklines

In the last decade, more than 100 offshore EPIC projects, including groundbreaking deepwater achievements
High quality drilling player onshore and in niches offshore Drilled over 7,300 wells of which 1,800 offshore
Technologies for Carbon Capture in oil refineries
Roma, Oct. 18, 2011
Saipem Experience on Carbon Capture and Sequestration (CCS)

SAIPEM has substantial know-how and experience in the entire CO2 capture, transportation and storage chain acquired providing engineering services to Eni and other O&G companies. Capture:
Post combustion (CO2 washing) Pre combustion (Steam reforming/gasification) Oxy-firing (Oxygen combustion) Environmental impact studies
Source
Source
Transportation:
Pipelines design & construction. Environmental impact studies.
Storage:
Geomechanical modelling and monitoring Well and reservoir modelling, Environmental and wellbore integrity monitoring Environmental impact studies
Roma, Oct. 18, 2011
Presentation Summary
Power Station vs. Refinery

Refinery Emission Sources CO2 Capture in the FCC unit CO2 Capture in Hydrogen Production CO2 Capture in Crude Heaters and Steam Boilers Overall approach
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Power Station vs. Refinery
Roma, Oct. 18, 2011
A sense of scale
Power stations are responsible for about 80% of CO2 emissions from stationary sources more than 10 billion tons/year Refineries are third (after cement production) with about 6% of emissions (0.8 billion tons/year) This justifies current focus on power production
Pressure of law-makers concentrated on power production. At the GHGT-10 conference >90% of capture work was related to capture in coal-fired power stations
800 MW NGCC Power Station 500 MW Coal Power Station Refinery processing 250,000 bpsd of crude
~ 2.8 MTPY of CO2 ~ 3.5 MTPY of CO2 ~ 4.5 MTPY of CO2
Emission for a refinery vary for different crudes, fuels and configuration
Roma, Oct. 18, 2011
Different issues and concerns

POWER STATION Single Source Fixed CO2 Concentration (4% for NGCC 12% for coal) Very fast and drastic changes in workload may be required Plot plan availability is not necessarily a concern REFINERY Multiple sources (20 or more stacks ) CO2 Concentration variable with source and feedstock Capture operation of the same type than usual refinery operation Plot plan availabilty is a key concern
Additional safety issues mainly related to use of chemicals

CO2 capture introduces new types of processes inside the power station
Additional safety issues mainly related to use of pure oxygen

Already includes process units using the same techniques than capture units
Roma, Oct. 18, 2011
Refinery Emission Sources
Roma, Oct. 18, 2011
Emissions vary for different crudes and refineries
LOW EMISSION REFINERY

100,000 BPSD LIGHT CRUDE No cracking No sulfur reduction Fuel: Natural Gas Few Heaters & Boilers (< 12) No Hydrogen production GHG emissions: < 1.2 MTPY
HIGH EMISSION REFINERY

100,000 BPSD HEAVY CRUDE Complex refinery with many different products Fuel: Fuel Oil Many Heaters & Boilers (> 50) Hydrogen production GHG emissions: > 4.8 MTPY
Source: ExxonMobil (2008)
Roma, Oct. 18, 2011
Refinery Carbon Sources

Two major emitters
Flue Gas Flue Gas Flue Gas Flue Gas
Reformer Feed
SMR
Heaters
Power Co-Gen Steam
FCC Regen
Air
Fuel
CCS will mostly be retrofit, with plot space issues Multiple capture technologies likely needed
Some easy CO2 but not a lot, since pure CO2 vents from hydrogen plants are disappearing as new PSA-based SMRs are built
Emerging resource (e.g. heavy oil) have larger carbon footprint and will increase emissions.
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Typical distributions of emissions

10-15% of emissions are caused by fuel combustion for power
generation 35-45% of emissions are caused by fuel combustion in process heaters (furnaces) and steam boilers 30-50% of emissions are single source from chemical units , depending on the refinery process scheme: Renerator of the Fluid Catalytic Cracking unit for FCC-based refineries Hydrogen production unit for hydrocracker-based refineries
FCC AND HYDROGEN MAIN SINGLE TARGETS FOR SUBSTANTIAL REDUCTION OF GHG EMISSIONS IN A REFINERY
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CO2 Capture in the FCC unit
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Overview of an FCC unit

Products - Gasoline - LPG - Propene
Flue gas 10 20 % CO2
REGENERATOR Air RISER
Steam
Feed - VGO - ATR
A unit processing 60,000 bpsd emits ~ 1,000,000 t/year of CO2

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Main technological options
Fluegas
D E
CO2
> 99% pure 90% recovery
Amine Absorption
Fluegas F
D E
CO2
96% pure >99 % recovery
Equipment list
A Waste Heat Boiler B SOx scrubber C Amine Unit D CO2 compressor E Dehydration (mol. sieve) F ASU G Recycle compressor
99.5% O2
Recycle
Oxy-combustion
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Some comparison among options

Energy consumption is higher for the post-combustion case
(typically 2.5-3.5 GJ/ton vs. 1.5-2.5 GJ/ton) Capital cost is higher for oxy-firing, mainly due to the cryogenic separation (Petrobras, 2008). CO2 avoidance cost is potentially lower for oxy-firing (Petrobras, 2008) Post-combustion requires plot plan close to the FCC unit (order of 50x50m). Oxy-firing does not, if 96% CO2 purity is acceptable Surely not acceptable for EOR (oxygen is the main impurity) Oxy-firing requires safe location for air separation unit and safety measures for pure oxygen piping.
Roma, Oct. 18, 2011
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The CCP Oxy-combustion FCC Demonstration Run
The CO2 Capture Project (www.co2captureproject.org) is undertaking a field demonstration of FCC regenerator oxy-firing with flue gas recycle.
Tests are taking place at a large pilot unit (33bbl/d of feed) at a Petrobras research complex in Parana state, Brazil.
Main goals of the project are: Test start-up and shut-down procedures Maintain stable operation in oxy-combustion mode Test different operating conditions and process configurations Obtain reliable data for scale-up
Source: Project Fact Sheet (www.co2captureproject.org)
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CO2 Capture in hydrogen production
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Steam Methane Reforming

Flue Gas
Steam
~ 765 kg CO2/ 1000 Ncu ft H2
SMR
Feed
Water Gas Shift
H2 Purification (PSA)
Product
Natural Gas
Fuel
Tail gas Air
Hydrogen product 99.9+% purity
Low energy usage compared with previous conventional design (MDEA washing) All CO2 emitted in the flue gas low partial pressure- even though ~ 60% is generated inside the process at high pressure
Post-combustion only option with this scheme

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Autothermal Reforming
H2O H2 O
CO2
Fuel
Syngas generation
H2, CO CO2, H2O
Water-gas shift
H2, CO2
CO2 removal
H2
O2 Air
Air Separation
N2
For large volumes, autothermal reforming (ATR) is generally lower cost than SMR. For a CO2 constrained enviroment ATR is always lower cost when capture is required. CO2 avoidance cost 50% lower for ATR/MDEA vs. SMR/PSA
SMR/MDEA avoidance cost is 30% lower than ATR/MDEA, but only process side CO2 is captured (source: Chevron,2008)
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CO2 Capture in process heaters & boilers
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Heaters & Boilers: a peculiar source of CO2

A large percentage of refinery CO2 emissions are generated by the combustion of fuel gas or fuel oil in crude heaters and steam boilers
In a world-scale refinery this emission source may account for more than 2 million tons/year.
Heaters & boilers are widely scattered in size and in refinery location.
Usually a few tens of units, but may be more than 50. May discharge to ten or more stacks located in different zones A single unit may roughly emit from 50,000 to 500,000 tons/year CO2 concentration in flue gas ranging from 4 to 10% vol., depending on the fuel used
CAN THIS SOURCE BE MITIGATED?
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Capture techniques applied to Heaters & Boilers

POST-COMBUSTION Very large and long ducts should be constructed to convey all of the effluents to a centralized post-combustion unit Alternatively several smaller units should be built close to each stack. Cost and lay-out considerations seem to preclude this approach. PRE-COMBUSTION All of the fuel could be conveyed to a single large-scale ATR unit, producing hydrogen to be used as fuel for all heaters & boilers No plot space needed near the existing units Retrofit of heaters and boilers may be needed for hydrogen burning. OXY-FIRING Today a single train of cryogenic air separation may produce up to 4000 tons/day of oxygen, roughly corresponding to 1 MTPY of emitted CO2 Part of the flue gas (> 50%) would be recycled to each unit for combustion temperature control Air in-leakage would lead to low CO2 purity (~ 80%) making a purification step necessary before transportation and storage need for local or centralized plot plan Retrofit of heaters and boilers may be needed for oxy-combustion.
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Overall approach to carbon capture in the refinery
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The Hydrogen-fired refinery

H2 O H2 O
CO2
Fuel
ATR
H2, CO CO2, H2O
Water-gas shift
H2, CO2
CO2 removal
O2 Hydrogen Air
Air Separation
N2
Flue Gas
To hydrotreating
Heaters
Power Co-Gen Steam
FCC Regen
Air
CO2-free gas to stack
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Current limitations to an hydrogen-fired refinery

Gas turbines may only burn fuels containing up to 50% of hydrogen Nitrogen from air separation may be used as diluent Advanced burners for 70-85% concentration are under development and should be available commercially by 2020. According to vendors, single line ATRs may be built up to about 500,000 Nm3/h of hydrogen. That would be enough for several refineries. Two parallel lines might be alternatively used. Hydrogen burning in boilers and heaters is technically feasible, but needs to be demonstrated at the tens of MW scale before commercial implementation.
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The Oxygen-fired refinery

Flue gas
CO2 CPU
Flue gas Flue gas
Reformer Feed
SMR
Heaters
Power Co-Gen Steam
FCC Regen
Fuel
O2 Oxygen
Air ASU Nitrogen
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Current limitations to an oxygen-fired refinery

The oxygen-fired refinery would only mitigate FCC, heaters and boilers emissions.
Hydrogen production and power generation would need separate capture
2-4 parallel air separation trains may be needed FCC regenerator oxy-firing still needs to be proven Oxyfiring of boilers already at the demo stage (30 MW) Oxyfiring of heaters still needs a dedicated development program
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The Complete Environmental Services Provider
THANK YOU FOR YOUR ATTENTION
Roma, Oct. 18, 2011
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Technologies for Carbon Capture in Oil Refineries

Ivano Miracca Saipem s.p.a.

Saipem Highlights Leading Global EP(I)C General Contractor

Full service EP(I)C provider

Over 120,000 km of land pipelines, sealines and trunklines

Roma, Oct. 18, 2011

Saipem Experience on Carbon Capture and Sequestration (CCS)

Pipelines design & construction. Environmental impact studies.