LINDE's activities to develop the CO2

purification for the Oxyfuel

combustion process
Roland Ritter, Linde AG
Wuhan, 29th October 2015
 Carbon Capture and Usage
Linde offers solutions in all three pathways

Linde
Portfolio
Technology Process

Gas CO2
ASU Gasifier CO Shift cleaning purification &
Pre-Combustion (Rectisol) compression
Feedstock CO2

Feedstock

CO2
Oxyfuel ASU Boiler DeSOx DeNOx purification &
compression
CO2

Feedstock
Post CO2
Combustion Boiler DeNOx DeSOx capture &
compression
CO2

Linde Engineering Dresden 2 Wuhan, 29.10.2015

 Linde' scope at Oxyfuel-Pilot Plant Schwarze
Pumpe/ Germany

Air Separation Unit- ASU

(Oxygen supply: 6600 Nm³/h)

Gas Processing Unit - GPU

(CO2 Purification and Liquefaction: 240 t/d)

Linde Engineering Dresden 3 Wuhan, 29.10.2015

 Pilot Plant Schwarze Pumpe
Linde's Project Milesstones

2006 Contract signature (Scope: Engineering, Procurement, Construction and Start-up)

2008 Mechanical Completion, Commissioning and Start-up

2008 Signature of Technology Partnership for ASU and GPU with VATTENFALL

2008 Service Agreement for maintenance and operation of the ASU and GPU signed by
Linde Gas

2010 Implementation and test of the DeNOx test facility (Linde Cold DeNOx - LICONOX®)

2011 Delivery of liquid CO2 to Ketzin (underground CO2 injection and migration)

2014 End of Project

Linde Engineering Dresden 4 Wuhan, 29.10.2015

 Oxyfuel technology
Air separation plant (pilot plant Schwarze Pumpe)

Client
Vattenfall
Location
Schwarze Pumpe/Germany
Process
Oxygen supply
Capacity
6 600 Nm³/h Oxygen
Purity
> 99.5 vol % O2
Scope of work
Turnkey plant
Start-up
2008

 Commercial available technology

Linde Engineering Dresden 5 Wuhan, 29.10.2015

 Main results Air Separation Plant

All guaranteed parameter were shown during operation

— Overall capacity, product flow rates
— O2, N2 purity and pressure a conventional and proven
— turn down and load change capability ASU design could be
— utility consumption applied, referenced also in
other areas

Learning's about some power related specialties

— The requirements for load following capability of ASUs for Oxyfuel Power Plants are
higher than for conventional applications. During the operation at Schwarze Pumpe
requested load changes between 4 and 8% could be verified and the applicability of
Cryogenic Air Separation Processes for Oxyfuel was confirmed
— uninterrupted product supply for different operating modes, coal and flue gas qualities
were successfully tested
— integration of the ASU operation, start-up and shut down procedures, were optimized
within the overall Oxyfuel Process
— Linde ASU technology ready for commercial application also in Oxyfuel and CCS

Linde Engineering Dresden 6 Wuhan, 29.10.2015

 Oxyfuel technology
CO2 purification and liquefaction plant (pilot plant)

Client
Vattenfall
Location
Schwarze Pumpe/Germany
Process
Drying, compression,
liquefaction, rectification with
CO2 recycling and liquid
storage
Capacity
7 000 Nm³/h flue gas
240 t/d CO2 liquid
Purity
> 99.7 vol % CO2
Scope of work:
Turnkey plant  Commercial available technology

Start-up: 2008
Linde Engineering Dresden 7 Wuhan, 29.10.2015
 Main results Gas Processing Unit (GPU)

All guaranteed parameter were shown during operation

— Overall capacity
— CO2 recovery rate based on long
experiences in
— CO2 purity design and operation
— turn down and load change capability of ASU and CO2
— utility consumption Plants

Learning's about some power related specialties like

— experiences for different cases, coal and flue gas qualities
— operation of GPU with all other processes within overall power plant configuration could
be verified
— load changes around 4%/ minute verified
— optimization of start-up and shut down procedures in combination with a power plant
— dryer adsorbents and corrosion resistance for CO2 plants

Linde Engineering Dresden 8 Wuhan, 29.10.2015

 Pilot Plant Schwarze Pumpe
Captured and liquified CO2 in Linde's GPU

t CO2 captured

12000
418
10000 10661
4735

8000

6000
3593
4000

2000
1824
91
0
2008 2009 2010 2011 2012 Total
Year of
Operation

Linde Engineering Dresden 9 Wuhan, 29.10.2015

 CO2 injection
Linde supplies CO2 for injection tests in Ketzin

Client
German Research Centre for Geosciences
GFZ, Potsdam, Germany
Location
Ketzin/ Germany
Capacity
3,600 kg/h CO2
pressure adjustable up to 100 bar
Purity
Food grade CO2
Scope of work
Turnkey plant
Start-up
2008

 since 2011 CO2 from Schwarze Pumpe was

injected

Linde Engineering Dresden 10 Wuhan, 29.10.2015

 Storage and Injection
CO2 injection pilot plant – Maxdorf/ Germany

Client
PEG (Gaz de France)
Location
Maxdorf/ Germany
Capacity
16 – 32 t/h CO2
from coal power plant
Purity
> 99.7 vol% CO2
Scope of work
Turnkey plant

Operation and CO2

injection were not
allowed by the federal
state Sachsen-Anhalt/
Germany by law

Linde Engineering Dresden 11 Wuhan, 29.10.2015

 Basic data of the Demonstration Plant in
Jänschwalde

Capacity: 3000 MW (el.) 6 blocks, 500 MW each

Construction: 1976… 1989
Project stopped in
Upgrades: 1995 (retrofitting of FGD)
Germany by political
since 1996 gradual upgrade of the turbines reasons – no public
Lignite Coal: 14 Mio t/yr (approx. 1 kg lignite coal per 1 kWh) acceptance
Efficiency: 35… 36 %
Emissions: approx. 1.1 kg CO2/ kWh

Construction of an Oxyfuel-
Demonstration Plant for
approx. 250 MWel at the
Jänschwalde Power Plant site

 Capture of
approx. 1,3 Mio t/yr CO2

Linde Engineering Dresden 12 Wuhan, 29.10.2015

 Development of a large scale concept
Study for 250 MWel Oxyfuel Demo-Plant
Jänschwalde
The detailed design of all equipment as well as the creation of an 3D model

– true to scale arrangement of all

equipment and connecting pipes
– integration of ASU and CO2-plant
in the whole demonstration plant
– assessment of accessibility to
equipment, machinery and
measurement points (operability
of controls and instruments,
assessment of maintenance
spaces etc.)
– assessment of mounting and
construction concepts
– dynamic simulation of ASU and
GPU and investigation of
behavior in overall plant scheme

Linde Engineering Dresden 13 Wuhan, 29.10.2015

 Principle units for Oxyfuel technology

Linde Engineering Dresden 14 Wuhan, 29.10.2015

 Development of the Linde-concept for Oxyfuel
technology

Linde Engineering Dresden 15 Wuhan, 29.10.2015

 LINDE-concept alkaline wash unit
LICONOX™ (“Linde cold DeNOx”)

NO and SO2 Oxidation: advantages: • pre-purified, compressed gas

NO+½ O2  NO2 • moderate temperature
SO2 + NO2  SO3 + NO • small gas stream (low volume flow rate)
Alkali based wash unit: • smaller equipment
• high conversation rate
SO2+ 2 NH3 + H2O  (NH4)2 SO3
• no acid mixture (corrosion problem)
SO3+ 2 NH3 + H2O  (NH4)2 SO4
Ammonia water …
NO + NO2 + 2 NH3 + H2O  2NH4NO2
— reaction of NO and NO2
2 NO2 + 2NH3 + H2O  NH4NO2 + NH4NO3
— reaction of SO2 and SO3
2 NO +O2 + 2 NaOH  NaNO2 + NaNO3 +H2O

2 NO2 + 2 NaOH  NaNO2 + NaNO3 +H2O results are nitrite and nitrate …
Regeneration/ reduction: — reaction to a mix of nitrogen and sulfur fertilizer
NH4NO2  N2 + 2 H20 (Nitrite-decomposition > 60°C) — reduction to N2 and H2O possible (De-nitrification)
Linde Engineering Dresden 16 Wuhan, 29.10.2015
 Alkaline wash unit with real flue gas from oxy-boiler
– installation in the CO2-pilot plant Schwarze Pumpe

capacity:

Atm.
200… 700 Nm³/h
30… 40 (80) °C
5… 20 bar

NO/ NO2-
concentration
adjustable
with additional
dosing (cylinder)

using of
15 wt%
ammonia water or
33 wt%
sodium hydroxide

Linde Engineering Dresden 17 Wuhan, 29.10.2015

 Development of the kinetic model

determination of kinetic rate constants NO-conversation versus pH-value

4 NO + O2 + 2 H2O + 4 NH3 → 4 NH4NO2

[NO2]/([NO]x[O2]) in dm³/mol
4 NO + 3 02 + 2 H2O → 4 HNO3
100%
NOx conversion pilot plant

75%

50%
Kinetic model confirmed
25%  Good correlation between measured
data and kinetic model
0%
0% 25% 50% 75% 100%
NOx conversion simulated

Linde Engineering Dresden 18 Wuhan, 29.10.2015

 Reduction of spent salt solution
(test phase in Schwarze Pumpe)
purified
CO2-Gas Regeneration/ reduction:
NH4NO2  N2 + 2 H2O (Nitrite-decomposition)
Make up Water

Nitrite-content after reduction versus temperature

800
Ammonia Water
700

Cooling Water pH 7.2

compressed 600
pH 7.6
CO2-Gas
pH 7.8
nitrite reduction 500

HNO2 mmol/ l
400

300
spent salt
solution 200
(nitrates)
100

0
0 50 100 150 200
possible reduction of spent salt solution: Temperture °C

 NO-NO2 removal with 15wt%- ammonia water  100% (Basis)

 NO-NO2 removal with 33wt%- sodium hydroxide  ca. 46%
 NO-NO2 removal with ammonia water and reduction  ca. 23%

Linde Engineering Dresden 19 Wuhan, 29.10.2015

 Increasing of CO2-recovery rate – using PSA-unit

CO2 Product to
Application for Product-Compression
requirement of high CO2 CW
Compressor Raw Gas from
recovery rates Drying Stage

maximum 99% Product-Pre-

Booster II/
Turbine II
Vent Gas for
Compressor Regeneration and
Heat
higher spec. energy Exchanger
Recycle before
Pre-compression
consumption (additional Pressure Swing
Adsorption Unit
recycle)

N2, O2, Ar

Possibility
to ASU

Separator II
Separator I

installation of a pressure swing adsorption unit

CO2-rich fraction for regeneration and fed back into
process before pre-compression
CO2-lean fraction could be fed to the ASU
Linde Engineering Dresden 20 Wuhan, 29.10.2015
 Linde partnering with Aerojet Rocketdyne on their
development of "Pressurized Fluidized Bed Combustion"

Source: ZEPSTM Plant Model: A High

Efficiency Power Cycle with Pressurized
Fluidized Bed Combustion Process” Poster
presented by Ganesan Subbaraman et al.,
Pratt & Whitney Rocketdyne.

Zero Emissions Power and

Steam (ZEPSTM) plant

Pilot plant 1 MWth in erection

phase: Ottawa/Canada
start-up: June 2016
— The ZEPSTM plant utilizes an oxy-combustion process with near stoichiometric coal combustion
in a pressurized fluidized bed that enables:
● High power conversion efficiencies
● Low electricity costs with CO2 capture
— Key technology elements of the ZEPSTM plant
● A novel, high heat flux, high carbon conversion, once-through, bubbling, pressurized bed
combustor (PFBC) with an in-bed heat exchanger
Linde Engineering Dresden 21 Wuhan, 29.10.2015
 Conclusions

The cooperation with Vattenfall and all other partners was a major step for Linde in
developing Oxyfuel-Technology

Linde's core technology like ASU and CO2 purification and liquefaction (GPU) could be
verified under real conditions of a lignite fired power plant.

Significant improvements (e.g. new DeNOx technology) to improve the overall Oxyfuel
Power Plant were developed and successful tested.

Special power plant requirements like fast load changes could be shown for ASU and GPU.

Concepts for a large size Demonstration plant (Jänschwalde) were developed and are the
basis for next projects

New oxyfuel-concept with pressurized fluidized bed will be developed and tested in Ottawa/
Canada).

 ASU and GPU are commercial available for Oxyfuel Power Plants and other applications

Linde Engineering Dresden 22 Wuhan, 29.10.2015

Thank you for your attention

Roland Ritter
Linde AG/ Linde Engineering Dresden
phone +49-351-250 3267
[Link]@[Link]
 CO2 capture unit and injection plant
Snøhvit Hammerfest/Norway

Client
StatoilHydro ASA
Location
Snøhvit Hammerfest/Norway
Process
BASF aMDEA®
Drying, precompression, liquefaction,
postcompression
Capacity
824 000 Nm3/h natural gas with
2 000 t/d CO2; high-dense CO2
Purity
> 99 vol % CO2
Use of CO2
Injection into 150 km pipeline for storage at
2 600 m deep
Scope of work
Turnkey plant
Start-up
2008

Linde Engineering Dresden 24 Wuhan, 29.10.2015