1876-6102 © 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).Peer-review under responsibility of the organizing committee of GHGT-13.doi: 10.1016/j.egypro.2017.03.1789

Energy Procedia 114 ( 2017 ) 6536 – 6542

ScienceDirect

13th International Conference on Greenhouse Gas Control Technologies, GHGT-13, 14-18 November 2016, Lausanne, Switzerland

Toolbox of effects of CO2 impurities on CO2 transport and storage systems Filip Neelea, Joris Koornneefa, Jana Poplsteinova Jakobsenb, Amy Brunsvoldb, Charles Eickhoffc*

aTNO, Utrecht, The Netherlands bSINTEF Energy Research, Norway

cProgressive Energy Ltd, United Kingdom

Abstract

There is a need to gather new knowledge on the fundamental properties of CO2 mixtures with impurities and their impact on the chain integrity and economics of Carbon Capture & Storage (CCS) chains. One of the main results from the FP7 IMPACTS project is the IMPACTS toolbox, which comprises new experimental data, thermodynamic reference models for CO2 mixtures relevant for CCS and the framework for CCS risk assessment taking Health Safety & Environment aspects, the impact of the quality of the CO2 and CCS chain integrity into account, and finally the recommendations report. © 2017 The Authors. Published by Elsevier Ltd. Peer-review under responsibility of the organizing committee of GHGT-13.

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1. Introduction

CO2 has been transported for the purpose of enhanced oil or gas recovery for decades, particularly in the USA. While abundance knowledge exists on the topic of CO2 transport and storage from research and learning-by-doing, it is well-accepted that there is a need to gather new knowledge on the fundamental properties of CO2 mixtures with impurities and their impact on the CCS chain integrity and economics.

The EU FP7 project IMPACTS [1] was aimed at research into the impact of impurities in captured CO2, from power plants and other CO2-intensive industries, on CO2 transport and storage. At the start of the project, the main uncertainties surrounding impurities in CO2 transport and storage were related to the following areas:

There was an incomplete understanding of the relation between impurities in the CO2 and the properties of the mixture. Experimental data on mixture properties were incomplete; there was a need for verified property models that cover relevant mixtures of CO2 and impurities;

There was a limited understanding of the effect of impurities on materials, equipment, processes, operation and safety procedures;

There was a need for a better understanding of the impact of impurities on storage integrity.

Knowledge about these issues is essential for safe and efficient transport and storage solutions for CCS.

* Corresponding author. Tel.: +31 88 866 4859. E-mail address: filip.neele@tno.nl

Available online at www.sciencedirect.com

© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).Peer-review under responsibility of the organizing committee of GHGT-13.

Filip Neele et al. / Energy Procedia 114 ( 2017 ) 6536 – 6542 6537

2. Objectives of IMPACTS project

The objective of the IMPACTS project [1, 2] was to develop a knowledge base on the relation between CO2 quality and design, construction and operation of CO2 pipelines and injection equipment. The following research objectives were addressed in IMPACTS:

To quantify fundamental properties (e.g. phase behaviour, thermodynamics, fluid flow, and chemical reactions) of relevant CO2 mixtures through modelling, experimental work, and collection of existing data.

To derive CO2 quality issues while considering integrity of the whole CCS chain. To provide recommendations for optimized CO2 quality on a case-by-case basis in the for CCS chains which are seen relevant

for large-scale deployment of CCS. To reveal the impacts of relevant impurities in the CO2 stream on the design and operation of the transport and storage

infrastructure through techno-economic assessments. To build knowledge critical for implementation of optimized safe and cost-efficient transport and storage of CO2

strengthening the competence within industry, academia and regulatory bodies .

The IMPACTS project did not aim to develop recommendations for CO2 quality; rather, the knowledge base developed in the project is to be used by CCS operators to make decisions about the CO2 quality in their system from an analysis of the trade-offs between CO2 quality and transport and storage infrastructure design. To this end, the IMPACTS project covered a range of technology areas, that are described in some detail below. The COORAL project in Germany [3] also studied the impact of impurities from a whole-chain perspective.

3. Aim of the Toolbox

The IMPACTS Toolbox provides an overview of and an introduction into the IMPACTS project. It provides a point of access to the results obtained in the project on the effects of impurities in the CO2 flow CCS infrastructure in a range of technology areas. The Toolbox highlights the main results and conclusions. For example, the Toolbox summarises and presents the new experimental data that has been developed within the IMPACTS project. This includes thermodynamic reference models for CO2 mixtures relevant for CCS, as well as the framework for CCS risk assessment that takes HSE aspects, the impact of the quality of the CO2 and CCS chain integrity into account.

The Toolbox is available online [4] and contains links to publicly available reports and publications from the project.

4. Key features of the IMPACTS Toolbox

The IMPACTS Toolbox [4] contains a summary collection of the primary results from the project. The contents of the Toolbox is summarized here by showing a series of highlights for each of the technology areas covered by the project.

4.1. Typical CO2 mixtures

The starting point in the project was an analysis of the range of impurity concentrations that could be expected for realistic combinations of emission sources and capture processes [5]. Fig. 1 shows the range of concentrations of the most common impurities; these ranges were used as guidance in the assessment of CO2 impurity impact in the technology areas covered in the project.

4.2. Thermophysical behavior of CO2 mixtures

A key effort in the project was to expand the volume and quality of thermophysical data and models of relevant CO2 mixtures [6, 7]. The project contributed to a new version of the TREND software from Ruhr University of Bochum [7], which contains the latest set of binary mixture data (part of which was collected in the IMPACTS project [6, 7, 8]. TREND can be linked to other modelling software, making it possible to include in CO2 transport and injection calculations the most up-to-date knowledge of the thermophysical behavior of CO2 mixtures. The software also includes a new phase stability algorithm, developed by Ruhr-Univesity Bochum, that automatically handles up to three phases in equilibrium (see [6]); this means that hydrate formation can also be accurately represented in, for example, pipeline flow assurance studies.

6538 Filip Neele et al. / Energy Procedia 114 ( 2017 ) 6536 – 6542

Fig. 1. Overview of combinations of emission source and capture process that produce CO2 mixtures with highest concentration of specific impurities.

Fig. 2 shows the mixtures that can currently be handled by the TREND software.

4.3. Transient fluid dynamics

The detailed properties of CO2 mixtures were used to compute transient phenomena in CO2 pipeline structures. It was found that impurities can significantly alter the behavior of the mixture, with important implications for the conditions at which hydrates form or for the development of running ductile fractures. This applies even for small quantities of impurities. A simplifying assumption that CO2 is pure can therefore lead to significant underestimation of the fluid pressure during the decompression, with consequences for the prediction of running ductile fractures. Fig. 3 shows the Toolbox entry for this work.

One conclusion from this work is that the cricondenbar pressure should be the design criterion for operation of CO2 pipelines, to avoid two-phase flow and running ductile fractures, to limit over-specification and to reduce costs [9].

Fig. 2. Binary CO2 mixtures covered by the TREND model, which was expanded with data during the IMPACTS project. The Toolbox provides a link to the TREND software.

WORST COMBINATIONS

Six combinations that produce the highest levels of impurities

[CO2] above 95%

Concentrations in ppmv or %

Water content not includedDefined by customer, not by capture process

Desulphurisation included

CO

2so

urce

Cap

ture

te

chno

logy

Coa

l-fire

d po

wer

pl

ant

Am

ine-

base

d ab

sorp

tion

Coa

l-fire

d po

wer

pl

ant

Am

mon

ia-b

ased

ab

sorp

tion

Coa

l-fire

d po

wer

pl

ant

Sele

xol-b

ased

ab

sorp

tion

Coa

l-fire

d po

wer

pl

ant

Oxy

fuel

co

mbu

stio

n

Nat

ural

gas

pr

oces

sing

Am

ine-

base

d ab

sorp

tion

Synt

hesi

s ga

s pr

oces

sing

Rec

tisol

-bas

ed

abso

rptio

n

CO2 99.8% 99.8% 98.2% 95.3% 95.0% 96.7%N2 2000 2000 6000 2.5% 5000 30O2 200 200 1 1.6% 5Ar 100 100 500 6000

NOx 50 50 100SOx 10 10 100CO 10 10 400 50 1000H2S 100 200 9000H2 1.0% 500

CH4 1000 4.0% 7000C2+ 5000 1.5%NH3 1 100

Amine 1

Post Post Pre Oxy Amine Amine

REPORT ON THE REFERENCE MODEL FOR THERMODYNAMIC PROPERTIES

D 1.2.6CaptureTransportStorage

Overview of the pure components and binary mixtures included in the model for the thermodynamic properties of CO2 -rich mixtures

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Fig. 3. Toolbox presentation of work related to the impact of impurities on transient phenomena in CO2 pipelines.

4.4. Impurities and corrosion

The presence of a significant level of water in the CO2 stream causes many problems in pipelines and injection wells and is probably the most important impurity to control. To avoid excessive corrosion and stress corrosion, water levels should be as low as possible to prevent corrosion or hydrate formation. CO2 streams should be dried to levels below 350 ppm H2O, (in some situations suggested to below 50 ppm) to prevent significant corrosion. Water concentrations should be below 250 ppm to ensure no hydrate formation (above 70bar and -30°C). Hydrogen and H2S levels should each be kept to below 100 ppmm if there is significant (>1000ppmm) moisture in the pipeline / injection systems (see [10]). Fig. 4 presents some of the corrosion results obtained in the project.

Fig. 4. Corrosion results presented in the Toolbox.

4.5. Impact of impurities on storage

Storage related research in IMPACTS included geochemical interaction between the CO2 mixture and the storage reservoir, and the impact of impurities on storage capacity [11]. In addition, an injection test of 95% CO2 plus 5% N2 was conducted at the Ketzin site [12]. Conclusions were that storage of impure CO2 in formations at depths of around 800 m or less is unlikely to be economic compared to the option of reducing impurities at the source. CO2 for storage in chalk fields should be cleaned upstream – detailed tests needed if impurities should be stored in chalk fields. Generally accepted safe limit for oxygen level in CO2 injected into hydrocarbon reservoirs is 10 ppm [11].

THE INFLUENCE OF CO2 MIXTURE COMPOSITION AND EQUATIONS OF STATE ON SIMULATIONS OF TRANSIENT PIPELINE DECOMPRESSION

Pipelines may need to be emptied (or decompressed) due to maintenance or be accidentally emptied due to a rupture.It is of interest to predict the temperature and pressure in the pipeline during a decompression for (at least) two specific reasons. First, as the pressure drops, the liquid will expand and eventually start to boil, which cools the pipe down. Low temperatures can be damaging to the infrastructure. Second, the pressure when the liquid starts to boil is relevant for running fractures. For these reasons, we need accurate mathematical models to predict the temperature and pressure during a decompression. A key component necessary to describe flow of CO2 mixtures is the thermodynamic model, which relates properties like pressure, temperature and density to each other.

Relevance

In this work, we examine whether it is beneficial to use highly accurate thermodynamic models (EOS-CG and GERG) instead of a much simpler model (Peng–Robinson) when predicting temperatureand pressure during a decompression. We also investigate whether the amount of other gases has any significant effect on temperature and pressure.

Description

To reports

Contact: Eskil Aursand, SINTEF, eskil.aursand@sintef.no

Further information

D 1.3.2

Our results show that for decompression, the choice of thermodynamic model matters much less than the amountof other gases. When the amount of other gases is increased, the boiling pressure can increase significantly, whichcan increase the risk of running fractures. It was found that the lowest temperature depends neither significantlyon the amount of other gases nor on the choice of thermodynamic model. For other CO2 pipeline considerations,however, the choice of thermodynamic model have larger impacts.

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CaptureTransportStorage

GENERAL CORROSION FROM CO2MIXTURES

D 1.4.2CaptureTransportStorage

Example results (10 test conditions in total): 1. Average corrosion rates2. XRD results of the

corroded samples 3. SEM images of the

corroded samples 4. Examples of 3D surface

morphology of cleaned samples

5. Photographic investigation of the corroded samples (not shown)

X60 X65

X70 X80

A1 A2

A3 A4

X60 X65

X70 X80

1

3

2

4

Highlight

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Fig. 5. Example slide from Toolbox that shows the impact of impurities on storage capacity. The effects shown are a combination of density decrease and displacement by the impurities. At shallow depths, 800 – 900 m, effects can be particularly significant when the critical point is shifted to higher pressure.

4.6. Techno-economical analyses of the impact of CO2 quality on transport and storage infrastructure

The aim of the IMPACTS project was to consider the entire CCS chain, from capture to storage, tob e able to study trade-offs between CO2 purity delivered by capture facilities and, e.g., material choice in downstream systems. Fig. 6 shows part of this trade-off: the cost of obtaining a specific CO2 purity at the capture plant. Examples are shown for N2 and water; the results are based on an estimated relative cost change, using an assumed reference concentration for either N2 or water and using public cost figures for the capture processes. More specific results can be found in [5, 13, 14].

Fig. 6. Examples of techno-economic trade-off study in IMPACTS. Left: trade-off related to N2 level; right: trade-off related to water content.

4.7. Risk assessment

The risk framework developed in IMPACTS used the purity levels derived from literature sources on existing or planned projects (see, e.g., [5, 13]) and concluded that there are no health issues presenting a ‘Red Line’ for specific impurities. At the levels being considered for the IMPACTS project the health impact of the CO2 always dominates that of the impurities. In addition, at the levels being considered for the IMPACTS project the environmental impact of the CO2 always dominates that of the impurities, and will normally be better than the “do nothing” option [15]. Fig. 7 shows an example of the risk material presented in the Toolbox.

EFFECT OF IMPURITIES ON STORAGE CAPACITY

Depth (m)reservoir

Coal-fired power stationPost-combustion ammonia

AquiferStorage capacity (Mt)

Pure Mixture Diff (%)800 14.1 13.9 -1.4900 15.9 15.7 -1.32000 34.4 34.2 -0.63400 57.0 56.8 -0.3

Coal-fired power stationOxyfuel Combustion

AquiferStorage capacity (Mt)

Pure Mixture Diff (%)14.1 7.8 --44.715.9 11.0 -30.8

34.4 30.7 -10.8

57.0 52.5 -7.9

2.5% N22.2% O2

1% N2

Example: Overall capacity of Aquifer storage by depthEffect of adding additional N2, O2 to mixture

Impurities used in model

Effect on density

Effect on critical point

Data from TNO using REFPROP

TECHNO-ECONOMIC ANALYSISCHAIN COST FUNCTION

D 2.2.2 / 3CaptureTransportStorage

1000 2000 5000 10000 20000 50000

104.35

104.40

104.45

104.50

104.55

104.60

104.65

104.70

104.75

104.80

IMPACTS SENSITIVITIES

Allowing a higher level of nitrogen allows for a cheaper ASUFurther tightening of the specification requires use of CO2 in lock-hoppers

Effect of Nitrogen & Water reduction on Pre-combustion Capture costs

Nitrogen level ppmm

Cos

t per

Ton

ne C

O2

Step change at 250ppmm with introduction of methanol dryingIncreasing opex costs to get moisture level down further

Water level ppmm20 50 100 250 500 1000

104.00104.10104.20104.30104.40104.50104.60104.70104.80104.90105.00105.10

TECHNO-ECONOMIC ANALYSISCHAIN COST FUNCTION

D 2.2.2 / 3CaptureTransportStorage

Filip Neele et al. / Energy Procedia 114 ( 2017 ) 6536 – 6542 6541

Fig. 7. Results related to risk assessment in the IMPACTS project, as presented in the Toolbox.

4.8. IMPACTS recommendations

The recommendations from the IMPACTS projects are derived from the results obtained in the technology areas addressed in the previous sections. the whole CCS chain analysis performed within the project resulted in recommendations at a more general level (see also [16], for a more extensive discussion). Some of these recommendations are:

There is no easy, one-size-fits-all solution for the design of a CCS chain or for the definition of CO2 impurities limits. It is generally more economic to clean up the CO2 stream at capture (upstream) than to deal with significant downstream

effects. Measurements of thermophysical properties of CO2 with impurities should be implemented in models and tools – this should

be a primary research focus in CCS. The best data and tools available should be used to design CCS chains on a case-by-case basis.

There are always trade-offs when selecting the optimum CO2 stream quality and deciding when and where to handle the impurities. These trade-offs are case-specific; the knowledge base developed in IMPACTS enables the assessment of the trade-offs for specific CCS chain conditions.

5. Conclusions

One of the main results from IMPACTS project is the IMPACTS toolbox, which gives an overview of and an introduction into the results of the project. The Toolbox is available online and links to the publicly available reports and publications from the project. The aim of the Toolbox is that it will be used by IMPACTS partners and CCS stakeholders as an introduction into the contribution of the IMPACTS project on the knowledge base on the relation between CO2 quality and the design and operation of CO2 transport infrastructure.

6. Acknowledgements

The research leading to these results has received funding from the European Union Seventh Framework Programme (FP7/2007-2013) under grant agreement n° 308809 (“Impact of the quality of CO2 on transport and storage”) as well as from Statoil Petroleum SA, Lundin Norway AS, Gas Natural Fenosa, MAN Diesel & Turbo SE, and Vattenfall AB.

References

[1] Lilliestråle A, Mølnvik M, Tangen G, Jakobsen JP, Munkejord ST, Morin A, Størset SØ, The IMPACTS Project: The Impact of the Quality of CO2 on Transport and Storage Behaviour, Energy Procedia, 51, 402-410, 2014.

[2] EU FP7 IMPACTS, The impact of the quality of CO2 on transport and storage behavior https://www.sintef.no/projectweb/impacts/. [3] Rütters H, Stadler S, Bäßler R, Bettge D, Jeschke S, Kather A, Lempp C, Lubenau U, Ostertag-Henning C, Schmitz S, Schütz S, Waldmann S, COORAL

team, Towards an optimization of the CO2 stream composition – a whole-chain approach, Int. J. Greenhouse Gas Control, in press, 2016. [4] Koornneef JM, Neele F, EU FP7 IMPACTS: Toolbox of effects of CO2 impurities on CO2 transport and storage systems, 2015. Available at:

http://www.sintef.no/globalassets/sintef-energi/impacts/d3-2-2-impacts-toolbox-.ppsx [5] Eickhoff C, Brown A, Neele F, Techno-economic issues and trade-offs for CO2 purity in CCS chains, Energy Procedia, this volume, submitted, 2016.

FRAMEWORK FOR RISK ASSESSMENT OF CO2 TRANSPORT AND STORAGE INFRASTRUCTURE

CO2, if inhaled in sufficiently high concentrations, can have toxicological effects on the human body. The hazardous aspect of CO2, combined with the very large quantities that will be contained within CCS systems create the potential that a leak from a CO2 system could pose a major accident hazard (MAH) (i.e. a hazard that could pose significant harm to humans or the environment). In addition, captured CO2 will not be 100% pure. The CO2 stream from capture plants will contain substances, such as CO, H2O, H2S, NOx, SOx, O2 and H2 that, although in very low levels, can change the properties of the CO2 stream and can change the likelihood and/or the consequences of CO2 system leaks.The goal of this report is to provide a framework for risk assessment for COtransport, with particular focus on CO2 with impurities.

Relevance

As a first step in the development of the risk assessment framework an overview of guidelines, recommended practices, reports and projects related to the risk management within CCS was developed. Particular focus has been given to CO with impurities and to what extent the methods in use are sufficient for analysing and managing risk related to handling large quantities of impure CO .The next step will be to utilise the framework assessing the impacts of impurities to the risk picture and ultimately to costs..

Description

To reports

Contact: Mark Spruijt, TNO, mark.spruijt@tno.nl

Further information

D 2.3.2

A significant amount of information, including guidelines, industry standards and legislation, exists worldwide and provides decision support for the design of pipelines carrying hazardous materials. This includes risk reduction measures; and requirements for risk assessment, risk criteria and the need or otherwise for further risk reduction. However, in most cases CO is not currently in the scope, but it is possible to apply many of the principles therein to pipelines containing CO , albeit with some caution.

In the absence of agreed guidance figures, this Deliverable makes reference to standards that could be used in system design to support a Safety Case which demonstrates that the risks are at an acceptable level.

It may be concluded that, at the levels being considered for the IMPACTS project, the impurities represent a lower risk to personnel than the CO itself.

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CaptureTransportStorage

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[6] Gernert J, Jäger A, Span R, Calculation of phase equilibria for multi-component mixtures using highly accurate Helmholtz energy equations of state, Fluid Phase Equilibria, 375, 209-218, 2014.

[7] Herrig S, Span R, Validation of the Current Version of the Reference Model for Thermodynamic Properties, IMPACTS report D1.2.5, 2013, available online at http://www.sintef.no/globalassets/project/impacts/d1-2-5-validation-of-the-current-version-of-the-reference-model-for-ther---.pdf.

[8] Yang X, Richter M, Wang Z, Li Z, Density measurements on binary mixtures (nitrogen + carbon dioxide and argon + carbon dioxide) at temperatures from (298.15 to 423.15) K with pressures from (11 to 31) MPa using a single-sinker densimeter, J. Chem. Thermodynamics, 9, 17-29, 2015.

[9] Aursand E, Aursand P, Hammer M, Lund H, The influence of CO2 mixture composition and equations of state on simulations of transient pipeline decompression, Int. J. of Greenhouse Gas Control, in press, 2016, http://dx.doi.org/10.1016/j.ijggc.2016.07.004.

[10] Xu M, Li W, Zhou Y, Yang X, Wang Z, Li Z, Effect of pressure on corrosion behavior of X60, X65, X70, and X80carbon steels in water-unsaturated supercritical CO2environments, Int. J. Greenhouse Gas Control, 51, 357-368, 2016.

[11] Waldmann S, Hofstee C, Koenen M, Loeve D, Liebscher A, Neele F, Physicochemical effects of discrete CO2-SO2 mixtures on injection and storage in a sandstone aquifer, Int. J. Greenhouse Gas Control, in press, 2016.

[12] Fischer S, Szizybalski A, Zimmer M, Kujawa C, Plessen A, Leibscher A, N2-CO2 co-injection field test at the Ketzin pilot CO2 storage site, Energy Procedia, 63, 2848-2854, 2014.

[13] Eickhoff C, Neele F, Hammer M, DiBiagio M, Hofstee C, Koenen M, Fischer S, Isaenko A, Brown A, Kovacs T, IMPACTS: economic trade-offs for CO2 impurity specifications, Energy Procedia, 63, 7379-7388, 2014.

[14] Skaugen G, Roussanaly S, Jakobsen J, Brunsvold A, Techno-economic evaluation of the effects of impurities on conditioning and transport of CO2by pipeline, Int. J. Greenh. Gas Control, in press, 2016.

[15] Raben I, Brown A, Eickhoff C, Neele F, Spruijt M, IMPACTS: framework for risk assessment of CO2 transport and storage infrastructure, Energy Procedia, this volume, submitted, 2016.

[16] Brunsvold A, Jakobsen JP, Mazzetti MJ, Hammer M, Eickhoff C, Neele F, Key findings and recommendations from the IMPACTS project. Int. J. Greenh. Gas Control, in press, 2016.