CCS for Industrial Sources
by
Gary Rochelle
Department of Chemical Engineering
University of Texas
Nearly half of the 123 Gt CO2 by 2050
should be from industrial applications
Mt CO2
Mt CO2
Mt CO2
Mt CO2
Mt CO2
Mt CO2
Note: Capture rates in MtCO2 /year
© OECD/IEA 2012
Direct CO2 Emissions from
Industrial Sources
(Data from IEA ETP 2012)
2
Potential Applications of CCS
Mostly Amine Scrubbing
• Power Plants – Coal and Gas
• Industrial gas-fired boilers and process heaters
– Iike power plants, but smaller
•
•
•
•
•
Lime and Cement
Steel Making
Catalytic Cracking
Fuel Gas Treating
H2 Production – gas, coal, biomass
– precombustion
• Fermentation
Gas-fired Boilers
• Used in chemical plants to make Steam
• Legacy (old) power plants
– Used for Peaking, not base load
– Investment not justified
• New for Alberta oil sands for superht stm
– Alberta expects CO2 reduction
– Waste heat from returning hot oil/water
• Usually includes heat recovery to 300-400F
• 7-9% CO2, 1-3% O2
• Energy source – Low P steam from cycle
Process Heaters
• In place of steam for heating (>600 F)
– Atmospheric and vaccuum crude distillation
– Other high boiling point HC’s
• In reactors for high T
– Olefin crackers – 1800F
– EB dehydrogenation to Styrene reactor – 1000F
– Steam Methane reforming to make H2
•
•
•
•
•
•
Frequently includes heat recovery, air preheating
3-7% CO2, Methane diluted by H2 etc., 1-5% O2
Clean, but hot (300-600F) gas
Distributed sources
Energy available as low pressure steam
Good candidate for Hydrogen produced by reforming CH4
– CH4+ 2H2O = 4H2 + CO2
– Capture and sequester CO2 in the reforming plant
Lime Plants
• Calcining Limestone
• CaCO3 = CaO + CO2
• Heat provided in fired rotary kiln
– By Coal – excess air required for combustion
• 20-30% CO2
– By natural gas
• 15-25% CO2
• Hot gas from kiln may provide stripping heat
Portland Cement
• Rotary kiln to calcine limestone & prepare clinker
• CaCO3 +SiO2 = CaSiO3 + CO2
• (Cement: CaSiO3 + H2O = CaSiO3.H2O)
– By Coal – excess air required for combustion
• 20-30% CO2
– By natural gas
• 15-25% CO2
Lime and Cement Considerations
• Energy Source
– No steam
– Waste heat from hot kiln exhaust if not used yet
– Electricity
• Good Candidate for Oxygen combustion
– Recycle gas around kiln
– Burn pure oxygen to increase capacity
– Less than one mole oxygen per mole CO2
• Flue gas can contain particulate, SO2, etc.
GLOBAL CCS INSTITUTE
CEMENT PLANT WITH TAIL END CAPTURE
9
GLOBAL CCS INSTITUTE
PARTIAL OXYCOMBUSTION
10
Iron and Steel
11
Steel Making
• Blast furnace gas
– Pure oxygen oxidizes coal coke to CO and CO2
• Most of CO2 emitted at power plant
– Oxidation of CO to CO2 is finished later.
• Air leaks in everywhere
• Final gas may have more or less O2 and
CO2 depending on collection system
• Waste heat may be readily available
ThyssenKrupp Steel Europe – Main CO2-Emitters
(schematically)
up to 20 mio t CO2 p.a.
CO2-emissions
x%
11%
30%
CO2
CO2
CO2
4%
% Carbon Input
4 Blast Furnaces
Coalinjection
0,1%
74%
~2%
BF Top Gas
Carbon in
liquid phase
9%
Cokeovengas
external
CO2
2 BOF Shops
Coal
Workshop CCS IEAGHG / VDEh
8. - 9. November
Prof. Dr. Gunnar Still
13
y% CO2-source
6 Power Plants
Coke
2 Coke Plant Batt
Absolut Part /t-CO2
48%
~9%
CO2
3 Hot Rolling,
3 Cold Rolling,
div. Annealing
etc.
1%
BOFgas
ThyssenKrupp Steel Europe
<0-1%
Catalytic Cracking in Refineries
• Used to reduce MW of crude oil to gasoline
• Cat cracking catalyst regenerated by air
combustion of C in fluidized bed.
• Any CO is later converted to CO2
• After particulate and SO2 removal, gas can
be 12-18% CO2
• Major point source of CO2 in refineries
• Waste heat, low P steam may be available
Other Applications
Application
CO2
(%)
Gas rate
(1e6 cfm)
O2
(%)
Coal power
12
2.5
5-8
Gas combined cycle
3-5
2.5
15
Gas conv boiler (tar sands)
7-9
1-2
1-3
Gas heater (Olefins)
5-7
0.2-0.5
2-5
CaO/cement
20-30
0.2-1
5-8
Iron & Steel
20-30
??
1-2
Natural Gas Treating
1-20
??
<0.1
GLOBAL CCS INSTITUTE
PROCESSES IN INDUSTRY THAT RESULT IN HIGH
CONCENTRATION CO2 OFF GAS
Activity
Source Stream
CO2 concentration (%; outlet)
Natural gas processing
Reservoir gas feed
95-100
Coal-to-liquids (CtL)
SMR/ATR, Gasifier
30-100
Ethylene oxide production
Gasifier
95-100
Ammonia production
Reactor (Haber-Bosch)
30-100
The technologies mainly used to separate CO2 from gas mixtures include:

Membrane separation;

Chemical solvents, including amine-based solutions (e.g. monoethanolamine
(MEA) and methyldiethanolamine (MDEA) and hot potassium carbonate
based processes (e.g. the Benfield™ process);

Physical sorbents (e.g. SelexolTM, Rectisol);

Pressure swing adsorption (PSA); and

Cryogenic separation.
16
GLOBAL CCS INSTITUTE
INDUSTRIAL HYDROGEN AND SYNGAS PRODUCTION (PRECOMBUSTION)
Note: SMR = Steam methane reforming; ATR = Auto thermal reforming; POX = Partial oxidation
Source: Zakkour and Cook, 2010
17
DCL
Solvent Based DCL Facility
Chinese owned developed catalyst
Reactor build by Chinese Heavy Industry
2 x Shell Gasifiers (@ ~315 TPD H2)
Slip stream CO2 Capture
18
Capture of CO2 from Steam
Air Products SMR providing
H2 to Valero Oil Refinery
Use of VPSA for CO2 capture
(90% recovery with 97% CO2
purity.
~1,000,000 t/y CO2 captured for
EOR application
Via Danbury Pipeline off to West
Hasting, Texas
Operation started in May 2013
19
GLOBAL CCS INSTITUTE
MAIN CHALLENGES FOR DEPLOYMENT OF CO2 CAPTURE FROM
INDUSTRIAL SOURCES
•
•
•
•
There are few incentives for CCS from industrial CO2 sources, even for the
low-cost options.
Policy for industrial CO2 reduction in industry is more challenging than in
the power sector with its domestic focus, because industry more often
operates on a global market, facing global competition.
– Thus, the industrial sectors require international agreements on policies
and measures to prevent such ‘carbon leakage’ and relocation of
industries.
Industrial CO2 streams are typically smaller than coal power plant CO2
streams, which may raise the cost per tonne of CO2 captured
The technologies required in industry are more diverse than in power
generation and therefore need a more diverse demonstration programme.
20