Innovative CO2 Capture Grant Agreement no: 241393

Final Publishable Report

REPORTING PERIOD DUE DATE TO THE EC PROJECT COORDINATOR

Reporting Period : M1– M48 27-02-2014 NTNU

PROJECT NAME

iCap

PROJECT FULL NAME

Innovative CO2 Capture

DURATION/START DATE

4 years/01-01-2010

Contents

1. EXECUTIVE SUMMARY .......................................................................................................................................... 3

2. PROJECT CONTEXT AND OBJECTIVES ............................................................................................................. 4

3. SCIENTIFIC &TECHNICAL RESULTS RESULTS/FOREGROUNDS .............................................................. 5

4.POTENTIAL IMPACT ............................................................................................................................................... 14

5. DISSEMINATION ..................................................................................................................................................... 15

6. LIST OF SCIENTIFIC PUBLICATIONS ............................................................................................................... 17

1. Executive Summary

CCS (Carbon Capture and Storage) is a cornerstone in the struggle for climate change

abatement. The current financial situation makes it crucial to focus on energy efficiency penalty,

and capital cost reduction. Post-combustion CO2 capture from fossil fuel must deal with low

flue gas CO2 partial pressure, 3.5-15 kPa. This limits membrane fluxes, solvent capacity, solvent

selection and increases energy requirements. Pre-combustion CO2 capture is marred with a large

number of processing steps, low hydrogen pressure, and high hydrogen fraction in the fuel.

Global deployment of CO2 capture technologies is restrained by the need for prior removal of

SO2.

The iCap project addresses a selection of research that is considered to be the most important

and promising with regard to improved energy efficiency and overall capture cost reduction.

Our postulate is that by addressing a selected range of the most important bottlenecks, we can

by each both reduce capital cost and improve energy efficiency, and achieve an accumulated

impact gain of a 40-45% reduction in the loss in power plant cost efficiency. iCap targets capital

cost reductions of 30-40% and a reduction in thermal and electrical energy use by 45% through

process intensification by the combined SO2 and CO2 capture, by increased capacity phase

change solvents, by elevated pressure desorption, by employing high flux membranes, and by

new cycles and better integration with the power production process.

The iCap project achievements are outlined below :

Selection, characterization and validation through pilot testing of an environmentally

benign, energy efficient multiphase post combustion solvent system. Pilot operation was

successfully completed covering a wide range of operating conditions. Thermodynamic and

kinetic models for both absorber and desorber conditions were implemented into in-house

simulators and validation against pilot data were performed. Regeneration heat requirement

below 2.4 MJ/kg CO2 captured was achieved experimentally and down to 2 MJ/kg CO2 by

simulation.

Development and characterization of two processes based on formation of CO2-hydrates.

These processes were shown not to be advantageous for post-combustion CO2 capture.

Development of fundamental models and tools capable of predicting thermodynamics of

multiphase solvent systems (e.g the two-liquid-phase system and systems forming hydrates).

Developed and test integrated multi component capture systems for combined SO2 and CO2

removal enabling significant process intensification and a total heat requirement of 2.3

MJ/kg and a total cost of 15 €/tonne CO2 avoided. Two systems, one amine and one

ammonia based system, were developed and their feasibility was demonstrated and validated

up to pilot plant scale.

Developed a PPO/PVA-HAPS1 based polymeric membrane with CO2 permeance 1.56

m3(STP)/(m

2 h bar) and CO2/N2 selectivity 294, twice the set initial goal. Long term

stability was demonstrated through gas permeation tests during 246 days.

Developed and test high flux, high stability membrane for steam methane reforming

applications based on SCZ material for hydrogen transport membranes (HTM). The material

has high stability at high temperatures and high CO2 and steam pressures, and shows high

hydrogen flux, close to that of the best known HTM materials reported in the literature.

Assessed novel power cycles and performed detailed techno-economic evaluations of the

developed capture technologies integrated in existing and new processes. Evaluations

showed a potential for achieving energy penalties of 6.8 % points from a coal fired power

plant without any heat integration. This is significant improvement over existing technology

and close to the target of 4-5% points.

2. Project Context and Objectives

The main objective of the iCap project is to develop new CO2 capture technologies that

individually and combined will enable highly efficient and cost effective production of electrical

power from fossil fuels with near zero emissions. The target is to reduce the CO2 capture energy

penalty to 4-5% points, about half of the penalty today, and to reduce the associated CO2 avoidance

cost to 15€/tonne CO2. Thereby the barriers for CCS deployment worldwide can be removed and

the technology deployment accelerated. This will be achieved by focusing on post combustion

technologies that can be used both for retrofit and for green field plants. The technologies to be

developed are highly innovative. Phase change solvents are used to concentrate up the CO2

captured, whereby the desorption heat requirement can be dramatically lowered while

simultaneously opening for the use of low-grade heat. In addition, the high CO2 concentrations

enables high pressure desorption and thus a reduction in recompression costs. Combined SO2 and

CO2 removal gives a high degree of process intensification with significant capital cost reduction.

Combined with low regeneration heat requirement it opens for CO2 capture technology deployment

in areas where SO2 control is not installed. High flux post combustion membranes offer a solvent

free and low efficiency penalty alternative and are particularly attractive in combination with the

new power cycles developed. Continuous industry lead evaluation and costing of the processes will

ensure the most effective progress of the project. Finally participation of CSLF countries, China and

Australia ensures exposure to and attention in these increasingly important geographical areas.

iCap is split into five work packages. The three main technology development work packages on

phase change solvents (WP1), membranes (WP4) and combined SO2/CO2 processes (WP3) form the

main body. All new thermodynamic modelling needed for these capture methods is performed in

WP2. The techno-economic evaluations in WP5 relate the separation techniques to the power

processes for integration, optimization, costing, and for validation of efficiency and energy savings

to be achieved. There are strong interdependencies between the WPs, e.g. the power processes may

pose individual and specific boundaries for integration of the separation processes which in turn

may put limitations on the separation process development in order to achieve the full potential in

improved energy efficiency and cost savings for the total integrated process.

3. Scientific &Technical Results results/foregrounds

WP1 Phase Change Solvents

The iCap project investigated two novel capture concepts into the post combustion technology

portfolio:

a) phase change solvents forming two liquid phases.

b) precipitating systems where CO2 is removed by hydrate formation enhanced by

thermodynamic promoters

The main purpose of operating with slurry systems or systems forming two liquid phases is to

achieve a concentrating up of the CO2 containing phase. When precipitation occurs the resulting

slurry can be thickened or filtered and a high CO2 concentration can be obtained. The same is the

case when two liquids form; one of the phases will be rich in CO2 and the other lean in CO2. By

limiting the further processing to liberate CO2 in a desorption stage to only a slurry or an extremely

rich liquid phase, the desorption becomes more energy efficient.

Phase change solvents forming two liquid phases

The iCap project has developed a novel absorbent system that forms two liquid phases at high

concentration and CO2 loading, with one phase containing CO2 at a very high concentration, this

resulting in low circulation rate, a more energy efficient CO2 desorption, and a potential for

obtaining the CO2 at elevated pressure

The DEEA/MAPA system was shown to have the desired properties with regard to forming two

liquid phases with high concentrations of CO2 in the lower phase, good chemical stability and good

potential for energy requirement reduction. This system was selected for further characterization.

For the individual components a large set of new equilibrium data was produced and on this basis

rigorous e-NRTL/e-UNIQUAC models were fitted. Further, a large number of equilibrium, kinetic

and physical property were been gathered for the mixed system. Based on the properties of the two

liquid phases, thermodynamic models for the mixed system were developed and used in the

SINTEF/NTNU in-house software CO2SIM to simulate both absorber and regenerator.

Modifications to the existing NTNU/SINTEF rig for pilot testing were performed, making it ready

for a multiphase solvent system. The rig is based on a full recycle of gas flow from the absorber to a

wash section, and then back to the absorber. Also the CO2 stripped off from the regenerator is

recycled back just before the circulation fan. Thus the rig is fully closed, making it particularly

suited for liquid/liquid systems that may have issues regarding solvent volatility.

The aqueous DEEA/MAPA solution was tested during a 4 month pilot plant campaign where 19

steady state points were achieved. As a base case a short additional MEA campaign was run. From

IC analyses on the upper phase, it is possible to conclude that practically all the MAPA is in the

lower phase. This is true for all loadings in the most interesting range. Therefore, if the loading is

defined as the number of moles of CO2 per mole of MAPA in the lower phase, displaying the

specific reboiler duty as function of this loading can be more easily compared with the MEA

campaign. The loading for MEA is calculated as the number of moles of CO2 divided by the

number of moles of MEA.

Pilot test results shown that we were able to operate down below 2.4 MJ/kg CO2 captured which

was significantly better than for the MEA campaign. Also the DEEA/MAPA campaign was not run

optimally as much light phase followed the heavy phase to the regenerator, thereby increasing the

sensible heat demand. As a general observation, the DEEA-MAPA system was easy to operate and

stripped very easily.

Figure 1. Modified pilot rig for phase change solvents

Experimental data from a pilot campaign for the system were validated towards the simulation

model implemented in CO2SIM. A total of 19 runs from the campaign were validated and

simulated with CO2SIM. It was concluded that a model of the DEEA/MAPA system was

successfully implemented in CO2SIM and can be used for further simulations of large scale plants.

Precipitated systems where CO2 is removed by hydrate formation

The aim of the iCap project was to create the fundamental theoretical background for and validate

this process by thoroughly investigating the thermodynamic and mass transfer phenomena at

laboratory scale and also carry out a first evaluation of the CO2 capture process by hydrates at

industrial scale.

The experimental work within iCap has shown than with the studied systems it is possible to

operate the hydrates formation at pressure below 5 bars and even at near atmospheric pressure.

Good N2/CO2 selectivity has been observed but with a CO2 content near 15 vol.%, which

corresponds to flue gases from coal power stations, a 2 step process appears necessary.

Nevertheless, if we operate at low pressure, hydrate storage capacity is low and by consequence

bulk reactor volume and flow rates are very high. To limit CAPEX and OPEX it would be

necessary to operate above 40 bars and in this case the energy penalty for flue gases conditioning

would be too high.

The main conclusion from the iCap project is that the hydrates processes are not adapted for CO2

capture in post-combustion. We recommend considering other applications for hydrates processes

such as CO2 capture in pre-combustion. For the future studies on hydrates processes, it would be

also very important to consider storage capacity as the main parameter for screening the different systems.

Environmental impacts of new phase change systems

A prerequisite of the new absorbent systems developed for phase change operation, is that they

should be environmentally benign. In addition to normal evaluations based on health and safety

norms, the systems selected for characterization have undergone testing for ecotoxisity and

biodegradation in accordance with the ISO/DIS Guideline 10253/OECD Guideline 306 standard

test procedures to ensure that they will be classified as environmentally safe.

Within this project the biodegradation and ecotoxicity in freshwater and marine environments were

determined for 5 solvents. These included the tertiary alkanolamine diethylaminoethanol (DEEA),

the secondary polyamine 3-amino-1-ethylaminopropan (MAPA), a mixture of DEEA and MAPA,

the quaternary ammonium compound tetra butyl ammonium bromide (TBAB) and the amino acid

beta-alanine in an alkaline solution. In addition, the ecotoxicity of aqueous ammonia was evaluated,

but not tested. The main outcomes of this study were:

All chemicals were biodegradable in freshwater or marine "ready biodegradability" tests, except

TBAB

All chemicals showed acute toxicities with EC50 > 10 mg/L in marine and freshwater

phytoplankton and invertebrate tests, indicating moderate ecotoxicity

Calculations of additive toxicity and comparison to measured results for the mixture of DEEA

and MAPA showed better agreement between the two approaches for marine than for

freshwater tests

The ecotoxicity of aqueous ammonia was also regarded as moderate, since this chemical

probably will appear as an ammonium salt at neutral pH.

Using a system for environmental classification and ranking of the iCap chemicals showed that

classification and ranking of these chemicals were comparable to the well-known CCS

alkanolamine monoethanolamine (MEA).

Determination of predicted no-effect concentrations (PNECs) for the iCap chemicals, based on

acute ecotoxicity results from the most sensitive tests, showed comparable or higher PNECs to

MEA, although the PNEC for TBAB was lower than for MEA.

WP2 Modelling of complex systems

WP2 developed thermodynamic models suitable for predicting, with limited information, the phase

behaviour of two-liquid phase systems and precipitating systems containing CO2 and various polar

solvents. This kind of modelling is essential for design and process modelling of capture based on

this technology.

The first of four tasks in WP2 models CO2 capture using gas hydrates. Gas hydrates are solid ice-

like structures formed from water and small molecules at moderate to high pressures. The

advantage is that they form preferentially with CO2 rather than with nitrogen, and (since they are

solids) they are easy to separate from the flue gas and remaining liquid. This tasks worked closely

with WP1 where the goal was to bring down the hydrate formation pressure using so-called hydrate

promoters.

The second task (W 2.2) models CO2 capture using a system which forms two liquid phases. Again,

the advantage is that CO2 enters one of the phases preferentially, enabling easier separation. This

task also worked closely with WP1 where appropriate solvents for forming the best liquid-liquid

separation were being identified. Rigorous models were developed, using the NRTL and e-NRTL

frameworks, to describe the vapor-liquid equilibrium of the binary systems: DEEA-H2O, MAPA-

H2O, MAPA-DEEA; the ternary systems: MAPA-DEEA-H2O, DEEA-CO2-H2O, as well as the

initial development of the model for the MAPA-CO2-H2O system. It is seen that the NRTL model

framework is well suited for the modelling of all the binary systems as well as the ternary amine

system without CO2. The e-NRTL framework further describes the DEEA-CO2-H2O system very

well but is not yet finished for the MAPA-CO2-H2O system. The soft models developed describe

the combined DEEA-MAPA-CO2-H2O well and was successfully implemented into CO2SIM. In

addition, a PSO (particle swarm optimization) based algorithm used to fit the NRTL and e-NRTL

parameters to the experimental data was developed.

The third task seeks to extend the models developed to elevated pressures, which may be attractive

under various capture scenarios. The final task models the effect of SO2 on the capture process.

This is an impurity often present in flue gas, and can affect the process in unexpected ways.

The main results of this are:

i) The development of a thermodynamic model for hydrate forming systems The model also

successfully models the effects of promoters which lower the formation of the gas

hydrates;

ii) The development of models of the liquid-liquid systems. The models can describe the

phase separation and individual phase equilibria in the two-liquid systems formed by

aqueous DEEA, MAPA and carbon dioxide;

iii) The production of new experimental data for both liquid-liquid and hydrate systems. This

has been carried out to an extent which enables development of models of these

processes;

iv) The development of a process concept and model for combined CO2-SO2 removal.

WP3 Combined SO2 and CO2 removal

The overall objective of WP3 is to develop, test and demonstrate a combined SO2 and CO2 capture

process with step-wise regeneration leading to one sulphur containing stream and one CO2 stream.

Central in this work package is the development of amine and ammonia based systems for the

combined removal and to demonstrate and validate this up to pilot plant scale.

For the amine based solvent, testing was performed on the pilot plant of CSIRO at AGL Loy Yang

power plant in Victoria, Australia. The testing was a joint effort of CSIRO and TNO in strong

collaboration with the Monash University, Gippsland Campus.

For the Ammonia based process, Tsinghua University completed and tested their system on a small

pilot plant. This pilot plant became operational at the beginning 2013. The small pilot plant was a

modification of an existing amine based absorption-desorption facility.

Testing of the CASPER process.

CASPER (CO2-capture And Sulphur Precipitation for Enhanced Removal) is a novel process,

developed within the iCap project, for simultaneous CO2 and SO2 removal from flue gas. The

process concept is based on reactive absorption of the acid gases in a solvent, using a potassium-

aminoacid based aqueous solution, and the precipitation of the sulphur as K2SO4.

Figure 2. The CASPER process.

The CASPER process was successfully tested in a pilot plant installation of CSIRO during

February and March 2013. The campaign took place at Loy Yang Power Plant in Victoria, Australia

(combined absorption and CO2 desorption part) and at Monash University, Gippsland Campus

(solvent regeneration step).

The baseline performance of 3M potassium β-alanate was satisfactory in comparison to the

experimental values obtained for MEA carbon capture processes in the same pilot plant installation.

Also, as expected, the SO2 was absorbed very efficiently into the solvent. The absorbed SO2 is

gradually converted via sulphite towards sulphate. The influence of different conditions on the

sulphur dioxide/sulphite- sulphate conversion rate were investigated. It was confirmed that SO2 and

higher concentration of oxygen (21%) together with presence of NOx can have a positive influence

on this chemical process.

Figure 3. The power plant with the pilot plant (red arrow) and a detailed picture of CSIRO’s PCC pilot plant at AGL

Loy Yang

The solvent was regenerated by removing the sulphate via precipitation as potassium sulphate and

subsequently reused in the second round of the pilot plant campaign. The actual solubility limits of

potassium sulphate were determined and compared with laboratory experiments. Observations of

the pilot plant campaign indicate a reasonable stability of the solvent.

The overall conclusion is that a proof of concept for the CASPER has been obtained. However,

more solvent optimization is needed to reduce energy consumption of the overall process as

compared to the state of the art solvent system MEA.Calculations made indicate that the CASPER

process will give a performance improvement of about 5.5% compared to MEA.

The ammonia based process.

The main research results on the combined capture of SO2 and CO2 using ammonia solvent are

summarized in this section.

Firstly, the kinetics and mass transfer of the combined process were studied in a wetted wall column

experimental system at different SO2 and CO2 loadings, ammonia concentrations, absorption

temperaturesand gas flow rates. It was observed that the CO2 and SO2 loadings have significant

effect on both the absorption of CO2 and SO2. This has to be controlled in the absorber to obtain a

high CO2 and SO2 recovery. The SO2 mass transfer does not decrease significantly when the CO2

concentration in the inlet flue gas increases. However, the SO2 concentration affects the CO2 mass

transfer significantly. A high ammonia concentration is beneficial for the combined absorption of

CO2 and SO2, and is more positive to the increase of the CO2 mass transfer coefficient. Both mass

transfer of CO2 and SO2 increase when the absorption temperature increases. The selectivity

absorption factor increases with increasing temperature. The CO2 mass transfer coefficient

increases marginally with increasing gas flow rate.

Secondly, the performance of the combined CO2 and SO2 capture process using aqueous ammonia

was studied in a lab-scale pilot plant at Department of Thermal Engineering, Tsinghua University,

China. The pilot plant tests involved individual CO2 and SO2 capture tests using aqueous ammonia

as the baseline and the combined CO2 and SO2 absorption and regeneration process tests. It was

observed that the pilot plant tests were repeatable and the gas inlet SO2 had no obvious effect on the

CO2 absorption efficiency. However, when the SO2 content accumulates in the aqueous ammonia

solvent, the CO2 absorption efficiency tends to decrease. The pilot plant performance also shows

that the ammonia loss is serious in both absorber and stripper gas outlet. This ammonia can react

with CO2 and water in the flue gas and precipitate solids in the condenser and pipes if the

temperature is low. This caused solid build-up that could block the stripper condenser and gas

looping pipes, leading to a shutdown of the pilot plant. Blockages also occurred in the CO2 analyzer

and gas flow rate meter tubing, leading to inaccurate readings and affecting long-term steady

operation of the pilot plant.

Thirdly, a rate-based model for a combined CO2 and SO2 absorption and regeneration process

using aqueous ammonia was developed and used to simulate results from the recent pilot plant tests,

evaluate the pilot plant performance, and to predict the unreachable pilot plant results caused by the

solid precipitation. The model was built based on the recent pilot plant setup and test parameters

using the Aspen Plus, mainly including a rate-based absorber unit and an equilibrium based stripper

unit, in which the thermodynamics, chemistry and kinetics of the NH3-CO2-SO2-H2O system were

specified. The predicted results show that the CO2 absorption efficiency decrease with an increase

in SO2 loading. Both the NH3 slip at absorber and stripper gas outlets were very high, CO2

regeneration energy decreases with SO2 loading accumulation in the looping solvent.

WP4 Highly efficient and long term stable membranes for CO2 capture

Activities in WP4 of iCap were focused on development of membrane technologies for CO2

capture, and they were divided into two types of membranes; Hybrid membranes for CO2 capture

for post combustion and hydrogen transport membranes (HTM) for separation of H2 in Pre-

combustion capture technologies.

The main objective was to develop high flux and stable membranes, suitable for the two operating

conditions. Hybrid or Mixed Matrix (polymer based + nanoparticles) membranes for selective CO2

separation are operated at low temperature (flue gas temperature) and separate CO2 from flue gas

mainly containing N2, O2, CO2 and H2O.

Hybrid or Mixed matrix membranes for CO2 Capture

Various polymers and nano-particles were examined in this project. One of these combinations was

shown to have outstanding performance as a low temperature CO2 selective membrane. This

membrane has a great potential for commercial development. Currently we have not published these

results but are developing a patent based on the results.

Hydrogen Transport membranes (HTM

The main objective was to develop high flux and stable membranes, suitable for the pertinent

operating conditions. Hydrogen transport membranes are considered for a catalytic membrane

reformer (CMR) operating at high temperature and pressure. These membranes were prepared from

ceramic H2 dense selective materials

Figure 4. Selected camera pictures of asymmetric tubular membranes successfully sealed to the ceramic

caps

The project has undertaken the ambitious tasks of developing high flux high stability membranes

for steam methane reforming application. This objective entailed the achievement of various

milestones, as follows:

Formulations of materials with improved stability verified at high temperature and

pressure

Synthesis, pressing and sintering of symmetric membranes with density above 95 %

Development of sealing procedures for mounting planar and tubular membranes in a

testing module

Manufacturing of thin film membranes coated on porous tubular supports with

adjustable porosity

Understanding of transport properties of the membrane materials

WP5 Technology evaluation, cost and efficiency estimations

WP5 was the system integrator, by using information from the other WPs of the project on

separation technologies development and performance, to evaluate power plant performance. The

models for the modified capture systems were extended to the entire power plant thereby enabling

assessment of performance for pulverised coal-fired supercritical hard coal and combined cycle gas

turbines. The relative operating costs of the new systems were compared with standard amine

systems and the overall economics assessed for a number of specific test cases.

Using models developed within iCap the “Cost of Electricity” (CoE) and “CO2-avoidance costs”

(AC) were evaluated for the reference capture process based on 30 wt.-% MEA as well as for the

novel capture processes. Furthermore, the CoE without CO2-capture was calculated to form a

quantitative basis for comparison.

The CASPER process and the liquid-liquid process show potential for reducing the CO2 avoidance

costs. Neither the hydrates, the low temperature membrane process nor the combined SO2/CO2

capture using aqueous ammonia process were deemed economically feasible compared with capture

processes based on wet chemical absorption. Technical difficulties, such as enormous auxiliary

demands or the necessity for very large heat exchange surfaces prohibit the use of the latter

concepts in practice for post-combustion CO2 capture from power plant flue gases.

As the absolute numerical results obviously depend on the degree of heat integration achieved and

the boundary conditions chosen for the assumed economics, while, at the same time, the novel

processes discussed here are themselves still in a stage of active research, the main target of this

work was not to supply absolute numbers for the final cost of electricity generation but rather a

realistic and reliable relative comparison among all capture processes tested. Towards this aim in all

simulations the components and equipment modelled reflected current industrial reality and

practice. For this, information and feedback from equipment manufacturers were obtained and

incorporated in the analyses for both the power plant and the downstream capture islands. In this

manner, as realistic results as possible could at the end be obtained.

The potential of the novel power cycles to mitigate the environmental impact from power

generation was evaluated on the comparison basis of generating 1 MWh of electricity in a typical

750 MW coal fired power plant. The complete chain of processes involved was included in the

evaluation, consisting of coal mining, coal transport, power plant with flue gas cleaning, solvent,

capture process and solvent waste treatment.

Although CO2 capture involves additional environmental impact on all environmental issues

considered in this study, with the exception of climate change, the impact is comparable with power

generation without CO2 capture. Key for the environmental impact is the associated increase in the

coal consumption, which requires mining and transport. Though the energy consumption is lowest

for liquid-liquid capture, the inherent uncertainties in the boundary conditions and data used still

prevent a conclusion on whether the liquid-liquid process is definitively better than the other

technologies, in terms of environmental impact. The influence of the source of the coal fuel is

significant. The differences among the mines plus the influences of transport distance are

comparable to the difference between capture and no capture. This means that there is a large

potential for improvement in the upstream processes. Note that the data for mining have an inherent

uncertainty too.Whereas the production and emission of solvent, as well as the treatment of solvent

waste, do not have a significant contribution to the overall environmental impact of power

generation with carbon capture, the influence of the source and transportation distances of the coal

are significant. This means that there is a large potential for improvement in the upstream processes.

As regards the emissions of nitrogen oxides, sulphur dioxide and ammonia, until good measurement

data become available, no conclusions can be drawn about the environmental preference among

MEA, liquid-liquid and CASPER based systems

4.Potential impact

Commercial deployment of new technologies requires a number of market driven mechanisms,

financial incentives (market push) and regulations (market pull), as well as technology

breakthroughs (technology push). CCS is a well-established subject on the European political

agenda and this ensures that market pull or/and push mechanisms are in place. However,

deployment of CCS projects faces a number of technical, economic and environmental challenges

with respect to costs, efficiency, and long-term underground storage. Therefore, industry supported

R&D activities for technology breakthroughs that will address these challenges are of critical

importance.

The technologies brought forward in iCap are partly of near term deployment nature. This is true for

both the phase change solvent and the combined CO2 and SO2 capture process. The phase change

solvent can operate in plants that distinguish themselves only marginally conceptually from today’s

plants. Apart from the smaller size, much of the equipment will be the same, or of a type already

existing. Thus, time from pilot plant testing at industrial scale to full scale deployment may not be

very long.

For the combined SO2 and CO2 capture, this is a process that has the potential to shorten the

deployment time significantly. Very few power plants in China, and even fewer in Australia, have

SO2 removal installed. For an ordinary amine plant, this will be a prerequisite and will lead to an

even larger hurdle for the deployment of CO2 capture technologies in these areas. The combined

process removes this hurdle and paves the way for CO2 capture, that otherwise might be regarded as

too costly.

5. Dissemination

1st Public Workshop EU-China workshop in CCS

An EU-China workshop in CCS was organized by NTNU. The event took place in Beijing 19-20th

of September 2011. The EU funded projects CACHET II and CO2pipeHAZ also took part in the

seminar. The event was jointly organized with the Chinese iCap partner THU (Tsinghua

University). Costs were shared within the iCap project partners having available budget for

dissemination. Some costs (dinner) were covered by Tsinghua University. Metrics of the event are

as follows:

Around 80 participants (Europe –China –Australia)

34 speakers

Opening + 7 technical sessions covering Policy, R&D, Fundamentals, Pilot & Demo

Activities

Proceedings/Presentations were uploaded on the public project website www.icapco2.org

2nd

Public Workshop (EU CCS Conference 2013)

The 2nd

Public Workshop was co-organized with other 7FP EU research projects: (CAPSOL,

DemoCLoCk, Innocuous and IOLICAP) funded by the European Commission through FP7. The

event was hosted by the Flemish Institute for Technological Research and held on May 28th and

29th, 2013, Antwerp Belgium. The event brought together representatives of academia, research

institutions and industrial stakeholders, thus forming a unique knowledge sharing experience for all

participants. A draft programme and invitation were issued December 2012, iCap contributed with

11 technical presentations and one keynote speech.

Conf. web: https://www.vito.be/VITOEvent/CCS2013/CCS-info.aspxx

iCap Website

The project website has been redesigned in order to increase the visibility of the project and its

results. www.icapCO2.org. Selected public summaries of technical reports all the public material

presented in various events has been collected and is accessible through the website.

6. List of Scientific Publications

Peer Reviewed Journal Publications

1. Herri, J.M., Kwaterski, M., 2012, Derivation of a Langmuir type of model to describe the

intrinsic growth rate of gas hydrates during crystallization from gas mixtures, accepted in

Chemical Engineering Science 2012, 81, 28-37

2. Herri J.-M., Bouchemoua A., Kwaterski , M., Fezoua A., Ouabbas Y., Cameirao A., Gas

Hydrate Equilibria from CO2-N2 and CO2-CH4 gas mixtures, – Experimental studies and

Thermodynamic Modelling, Fluid Phase Equilibria, Vol. 301, pages 171-190, 2011

3. Peter Jørgensen Herslund, Kaj Thomsen, Jens Abildskov and Nicolas von Solms,

”Thermodynamic and Process Modelling of Gas Hydrate Systems in CO2 Capture

Processes,” J. Chem. Thermodynamics 48 (2012) 13-27

4. Peter Jørgensen Herslund, Kaj Thomsen, Jens Abildskov, Nicolas von Solms, Aurélie

Galfré, Pedro Brântuas, Matthias Kwaterski, Jean-Michel Herri, Thermodynamic promotion

of carbon dioxide–clathrate hydrateformation by tetrahydrofuran, cyclopentane and their

mixtures, Int. J. Greenhouse Gas Control 17 (2013) 397

5. Peter Jørgensen Herslund, Kaj Thomsen, Jens Abildskov, Nicolas von Solms, ”Application

of the Cubic-Plus-Association (CPA) Equation of State to Model the Fluid Phase Behaviour

of Binary Mixtures of Water and Tetrahydrofuran,” Fluid Phase Equilib. 356, 209 (2013)

6. Arshad M.W., Fosbøl P.L., von Solms N., Svendsen H.F., Thomsen K., “ Heat of absorption

in phase change solvents: 2-(Diethylamino)ethanol and 3-(methylamino)propylamine”, J.

Chem Eng. Data., 2013, 58, 1974-1988

7. Muhammad Waseem Arshad, Philip Loldrup Fosbøl, Nicolas von Solms, and Kaj Thomsen,

“Freezing Point Depressions of Phase Change CO2 Solvents,” J. Chem. Eng. Data, 58, 1918

(2013).

8. Monteiro, J.G.M.S., Pinto, D.D.D., Zaidy, S.A.H., Hartono, A., Svendsen, H.F., 2013. VLE

data and modelling of aqueous N,N-diethylethanolamine (DEEA) solutions. International

Journal of Greenhouse Gas Control 19, 432-440.

9. Hartono A., Saleem F., Arshad M.W., Usman M., Svendsen H.F., “Binary and ternary VLE

of the : 2-(Diethylamino)ethanol(DEEA) / 3-(methylamino) propylamine(MAPA) / water

system”, Chem Eng. Science, 2013, 101, 401-411

10. Ciftja A.F., Hartono A., Svendsen H.F., “Experimental study on phase change solvents in

CO2 capture by NMR spectroscopy”, Chem. Eng. Sci., 102(2013),378-386

11. Monteiro, J.G.M.S., Pinto, D.D.D., Knuutila H.K., Svendsen, H.F., 2014. Kinetics of CO2

Absorption by Aqueous 3-(methylamino)propylamine Solutions: Experimental Results and

Modelling. Under submission

12. Pinto D.D.D, Juliana G. M.-S. Monteiro, Birgit Johansen, Hallvard F. Svendsen, Hanna

Knuutila, Density measurements and modelling of loaded and unloaded aqueous solutions

of MDEA (N-Methyldiethanolamine), DMEA(N,N-Dimethylethanolamine), DEEA

(Diethylethanolamine) and MAPA (N-Methyl-1,3-diaminopropane), Under submission

13. Arshad, M. W.; Svendsen, H. F.; Fosbøl, P. L.; von Solms, N.; Thomsen, K.

Equilibrium Total Pressure and CO2 Solubility in Binary and Ternary Aqueous Solutions of

2-(Diethylamino)ethanol (DEEA) and 3-(Methylamino)propylamine (MAPA). J. Chem.

Eng. Data, DOI: 10.1021/je400886w

14. Galfré, A., Cameirao, A., Chauvy, F., Lallemand, A., Herri, J.-M., 2013, Clathrate

hydrates equilibrium points for carbon dioxide and nitrogen gas mixture in presence of

cyclopentane in water emulsion, accepted to Chem. Engng. Science

15. Peter Jørgensen Herslund; Kaj Thomsen; Jens Abildskov; Nicolas von Solms, “Modelling of

Cyclopentane Promoted Gas Hydrate Systems for Carbon Dioxide Capture Processes”

submitted to Fluid Phase Equilibria (2013)

16. Peter Jørgensen Herslund; Kaj Thomsen; Jens Abildskov; Nicolas von Solms, “Modelling of

Tetrahydrofuran Promoted Gas Hydrate Systems for Carbon Dioxide Capture Processes”

submitted to Fluid Phase Equilibria (2013

International conference proceedings

1. Monteiro, J M. M-S., Pinto D.D.D, Luo X., Knuutila H., Hussain S., Mba E., Hartono A.

and Svendsen H.F. , “Activity based kinetics of the reaction of CO2 with aqueous amine

systems . Case studies: MAPA and MEA”, Energy Procedia, 37(2013), 1888-1896

2. Liebenthal, U.; Pinto, D.; Monteiro, J.; Hallvard, F.; Kather, A.: Overall process analysis

and optimisation for CO2 capture from coal fired power plants based on phase change

solvents forming two liquid phases. Energy Procedia, Volume 37, 2013, Pages 1844-1854

3. Pinto D.D.D, Monteiro, J M. M-S., Bersås A. Haug-Warberg T., and Svendsen H.F. ,

“eNRTL parameter fitting procedure for blended amine systems: MDEA-Pz case study”,

Energy Procedia, 37(2013), 1613 1620

4. Arshad M.W., von Solms N., Thomsen K. and Svendsen H.F., “Heat of absorption of CO2

in aqueous solutions of DEEA, MAPA and their mixture”, Energy Procedia, 37(2013), 1532-

1542

5. Arshad, M. W.; Fosbøl, P. L.; von Solms, N.; Svendsen, H. F.; Thomsen, K. Equilibrium

Solubility of CO2 in Alkanolamines. Submitted to Energy Procedia.

6. Peter Jørgensen Herslund, Kaj Thomsen, Jens Abildskov and Nicolas von Solms,

”Thermodynamic and Process Modelling of Gas Hydrate Systems in CO2 Capture

Processes,” International Conference of Gas Hydrate, ICGH 2011, Edinburgh, Scotland,

United Kingdom, July 17-21, 2011 (proceedings, paper ID 733)

International Conference Presentations

1. Hallvard Svendsen, “iCap – a project overview”, European Conference on CCS Research,

Development and Demonstration, London, 24-26 May 2011

2. Svendsen H.F. Monteiro J.G.M.-S. and Pinto D.D.D.”Phase Change Solvents”, EU–China

Workshop on Innovative CCS Technologies, Beijing, 19–20 September 2011

3. Liebenthal, U.; Kather, A.: Integration of Post-Combustion CO2 Capture Processes into

Coal-Fired Steam Power Plants. EU-China Workshop on Innovative CCS Technologies,

Beijing, China, 2011

4. Monteiro, J.G.M.-S., Pinto D.D.D., Hartono A., Svendsen H.F., “Reactive absorption of

CO2 into aqueous solutions of DEEA”, TCCS6, June 2011

5. Pinto D.D.D., Monteiro, J.G.M.-S., Bruder P., Zaidy, S.A.H., Jonassen Ø., Hartono A.,

Svendsen H.F., “Correlation and Prediction of Vapor-Liquid-Liquid Equilibrium using the

e-NRTL model applied to the MAPA-DEEA-CO2-Water System”, TCCS6, June 2011

6. Monteiro, J.G.M.-S., Pinto D.D.D., Zaidy, S., Hartono A., Svendsen H.F., “MAPA

kinetics”, Joint Seminar on CO2 Absorption Fundamentals, Trondheim, June 14th 2011

7. Pinto, D.D.D., Monteiro, J.G.M.-S., Bruder P., Zaidy, S.A.H., Jonassen Ø., Hartono A. and

Svendsen H.F, “Multiphase solvent for CO2 absorption”, Joint Seminar on CO2 Absorption

Fundamentals, Trondheim, June 14th 2011

8. Kwaterski, M. Herri, J.M., Modelling gas hydrate equilibria using the electrolyte two-liquid

(ENRTL) model, International Conference of Gas Hydrate, ICGH 2011, Edinburgh,

Scotland, United Kingdom, July 17-21, 2011

9. Kwaterski, M. Herri, J.M., Thermodynamic modelling of gas semi-clathrates hydrates using

the Electrolyte NRTL model, International Conference of Gas Hydrate, ICGH 2011,

Edinburgh, Scotland, United Kingdom, July 17-21, 2011

10. Bouchemoua, A., Brantuas, P., Herri, J.M., Equilibrium data of CO2-based based semi-

clathrates from quaternary ammonium solutions, International Conference of Gas Hydrate,

ICGH 2011, Edinburgh, Scotland, United Kingdom, July 17-21, 2011

11. Peter Herslund and Nicolas von Solms, “Modeling Carbon Dioxide Capture from Flue

Gases using Gas Hydrates“, EU–China Workshop on Innovative CCS Technologies

Beijing, China, 19–20 September 2011

12. Peter Jørgensen Herslund, Kaj Thomsen, Jens Abildskov and Nicolas von Solms,

”Thermodynamic and Process Modelling of Gas Hydrate Systems in CO2 Capture

Processes,” International Conference of Gas Hydrate, ICGH 2011, Edinburgh, Scotland,

United Kingdom, July 17-21, 2011 (proceedings)

13. Muhammad Waseem Arshad and Kaj Thomsen, “Freezing Point Depression of Aqueous

Solutions of DEEA, MAPA and DEEA-MAPA with and without CO2 Loading,” Efficient

Carbon Capture for Coal Power Plants, June 20 - 22, 2011, Frankfurt

14. Marie Laure Fontaine, Yngve Larring, Marit Stange, Paul Inge Dahl, Florian Ahouanto,

Partow P. Henriksen, Rune Bredesen Development of high temperature ceramic

membranes for enhanced steam methane reforming by hydrogen removal , EU–China

Workshop on Innovative CCS Technologies, Beijing, China, 19–20 September 2011

15. Liebenthal, U.; Pinto, D.; Monteiro, J.; Hallvard, F.; Kather, A.: Overall process analysis

and optimisation for CO2 capture from coal fired power plants based on phase change

solvents forming two liquid phases. 11th International Conference on Greenhouse Gas

Technologies (GHGT11), Kyoto, Japan, 21 November 2012

16. Pinto D. D. D., Monteiro J. G.M.-S., Bersås1 A., Haug-Warberg T., Svendsen H F., eNRTL

parameter fitting procedure for blended amine systems: MDEA-PZ case study, 11th

International Conference on Greenhouse Gas Control Technologies(GHGT11), 18 ‐ 22

November 2012, Kyoto, Japan

17. Monteiro, J.G.M.-S.1, Pinto D.D.D.1, Luo X.1, Knuutila H.1, Hussain S.1, Mba E.1,

Hartono A.1, Svendsen H.F.1, Activity-based Kinetics of the Reaction of Carbon Dioxide

with Aqueous Amine Systems. Case studies: MAPA and MEA, 11th International

Conference on Greenhouse Gas Control Technologies(GHGT11), 18 ‐ 22 November 2012,

Kyoto, Japan

18. Monteiro, J. G. M.-S. M., Pinto, D. D. D., Knuutila, H., Svendsen, H. F. Modeling

investigations on MAPA kinetics. University of Texas conference on Carbon Capture and

Storage (UTCCS1) – January, 25th

, 2012

19. Nicolas von Solms, Modelling and measuring promoted hydrate formation for CO2 capture,

presented at AIChE conference, San Francisco, November 2013

20. Liebenthal, U.: iCap WP5 – Overall process evaluation of novel capture technologies. CCS

Conference 2013, Antwerp, Belgium

21. Monteiro J. G. M-S., Diego D.D. Pinto and Hallvard F. Svendsen, Kinetics and

Thermodynamics of MAPA and DEEA, European Conference on Carbon dioxide Capture

and Storage, CCS2013, Antwerp, Belgium, 28 and 29 May 2013

22. Brakstad O.G., Kristin G. Lauritsen and Thor Mejdell, Biodegradation and ecotoxicity

testing of solvent systems, European Conference on Carbon dioxide Capture and Storage,

CCS2013, Antwerp, Belgium, 28 and 29 May 2013

23. Svendsen H.F., Solvents for CO2 absorption; an overview and status, European Conference

on Carbon dioxide Capture and Storage, CCS2013, Antwerp, Belgium, 28 and 29 May

2013

24. Diego D. D. Pintoa, , Juliana G. M.-S. Monteiro

a, Anita Bersås

a, Tore Haug-Warberg

a,

Hallvard F. Svendsen H.F., eNRTL Parameter Fitting Procedure for Blended Amine

Systems: MDEA-PZ, a Case Study, European Conference on Carbon dioxide Capture and

Storage, CCS2013, Antwerp, Belgium, 28 and 29 May 2013

25. Monteiro JGM-S1, Pinto DDD

1, Luo X

1, Knuutila H

1, Hussain S

1, Mba E

1, Hartono A.

1,

Svendsen H.F., Activity-based Kinetics of the Reaction of CO2 with AqueousAmine

Systems. Case studies: MAPA and MEA, European Conference on Carbon dioxide Capture

and Storage, CCS2013, Antwerp, Belgium, 28 and 29 May 2013

26. Diego D.D. Pinto, Hanna Knuutila, Juliana G. M.-S. Monteiro and Hallvard F.

SvendsenPilot campaign for phase change solvent, European Conference on Carbon

dioxide Capture and Storage, CCS2013, Antwerp, Belgium, 28 and 29 May 2013

27. Arshad M. W., Nicolas von Solms, Kaj Thomsen, Hallvard Fjøsne Svendsen, Heat of

Absorption of CO2 in Aqueous Solutions of DEEA, MAPA and their Mixture, European

Conference on Carbon dioxide Capture and Storage, CCS2013, Antwerpen, Belgium, 28

and 29 May 2013

28. Monteiro J. G. M.-S., Majeed H., Hussain S., Knuutila H., Svendsen H.F., Reactive

Absorption of CO2 into aqueous blends of DEEA and MAPA, TCCS7, Trondheim, June

2013

29. Pinto D.D.D., Thea W. Brodtkorb, Fridtjof Henriksen, Solrun J. Vevelstad, Eirik F. da Silva

and Hallvard F. Svendsen, Modeling MEA Degradation, TCCS7, Trondheim June 2013

30. Ciftja A.F., Ardi Hartono and Hallvard F. Svendsen, NMR Work on Phase Change Solvents

for CCS, TCCS7, Trondheim June 2013

31. Diego D. D. Pinto, Hanna Knuutila, and Hallvard F. Svendsen, Pilot plant campaign for

CO2 capture: evaluation of phase change solvent system, PCCC2, Bergen September 2013

32. Monteiro, J.G.M.-S.; Gupta, M.; Hartono, A.; da Silva, E. F.; Knuutlia, H.; Svendsen H.F.,

Reviewing the N2O Analogy, PCCC2, Bergen September 2013

33. Monteiro, J.G.M.S., Hammad, M., Knuutila, H., Svendsen, H.F., 2013. Modeling the

absorption of CO2 into aqueous blends of DEEA and MAPA. Oral presentation at the

AIChE Annual Meeting held at November 7, 2013, in San Francisco, USA.

34. Pinto D. D. D., Monteiro J.G.M.S, Knuutila H.K., Tobiesen F.A., Mejdell T. and Svendsen

H.F. (2013), Simulation of a Phase Change System for CO2 Capture. Oral presentation at

the AIChE Annual Meeting held at November 8, 2013, in San Francisco, USA.

35. Arshad, M. W.; Fosbøl, P. L.; von Solms, N.; Svendsen, H. F.; Thomsen, K. Vapor-Liquid

Equilibrium of CO2 with Aqueous Solutions of DEEA, MAPA and their Mixture, 2nd Post

Combustion Capture Conference (PCCC-2), Bergen, Norway, 17-20 September 2013. (Oral)

36. Arshad, M. W.; Fosbøl, P. L.; von Solms, N.; Svendsen, H. F.; Thomsen, K. Equilibrium

Solubility of CO2 in Alkanolamines, 7th Trondheim CCS Conference (TCCS-7),

Trondheim, Norway, 4-6 June 2013. (Poster)

37. Hartono, A.; Fahad. S.; Arshad, M. W.; Svendsen, H. F. Binary VLE of DEEA/H2O,

MAPA/H2O and DEEA/MAPA Systems, 7th Trondheim CCS Conference (TCCS-7),

Trondheim, Norway, 4-6 June 2013. (Oral)

38. Arshad, M. W.; von Solms, N.; Svendsen, H. F.; Thomsen, K. Heat of Absorption of CO2 in

Aqueous Solutions of DEEA, MAPA and their Mixture, GHGT-11, Kyoto International

Conference Center, Japan, November 2012. (Poster)

International technical seminars

1. Liebenthal, U.: Die dritte Generation der Post-Combustion Capture Verfahren. COORETEC

AG2, March 2010, Gelsenkirchen, Germany

2. Monteiro, J.G.M.-S., Pinto D.D.D., Zaidy, S., Hartono A., Svendsen H.F., “MAPA

kinetics”, Joint Seminar on CO2 Absorption Fundamentals, Trondheim, June 14th

2011

3. Pinto, D.D.D., Monteiro, J.G.M.-S., Bruder P., Zaidy, S.A.H., Jonassen Ø., Hartono A. and

Svendsen H.F, “Multiphase solvent for CO2 absorption”, Joint Seminar on CO2 Absorption

Fundamentals, Trondheim, June 14th

2011

4. Svendsen H. F., Phase change solvents; can they deliver?, Technoport invited lecture,

Trondheim April 2012