APPLICATION NOTE

INDUSTRIAL PROCESS & EMISSIONS

PROCESS: CARBON CAPTURE AND STORAGE

INTRODUCTION USEFUL LINKS

Carbon Capture and Storage (CCS) technologies aim to capture carbon
dioxide (CO2) emissions from power plants and heavy industry before
transporting it by pipeline or ship and storing it underground in, for
example, empty oil and gas fields. The driver behind this method is to
reduce the mass of CO2 that enters the atmosphere and contributes to
global warming and ocean acidification. The technology can be used in
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energy production facilities, and other industrial processes, wherever large guidance

CO2 quantities are produced. Different CCS technologies allow retrofitting

to existing plants and integrating in new plants.
Carbon Capture and Usage (CCU) aims to use the captured CO2 emissions
as a source for manufacturing of fuels, carbonates, polymers and other
chemicals, and contribute to a circular economy. In general, CCU is less
advanced in the industrial application than CCS and requires continuing
research and development. That said, CCU is already used on an industrial
scale in the European Union (EU) in the fertilizer industry for the production Watch our videos
of melamine and urea-based glues and resins, with around 1.8 Mtpa
(millions of tonnes per annum) of CO2 captured from steam methane
reforming (SMR) during the ammonia (NH3) production [Fertilizers Europe/
European Gas Regulatory Forum, 2019]. CCU is also used in the production
of calcium carbonate, where CO2 reacts with NH3 to produce lime which
can be mixed with calcium nitrate to produce calcium ammonium nitrate, a
popular nitrogen fertilizer used in the EU.
Due to the CO2 emissions exceeding the current expectations of CO2 usage
market development, CCU is considered a complementary alternative
to CCS only. Depending on the source the expected market potential is
approximately 200 MtCO2/y for CO2 utilisation [Aresta et al. 2013] and
approximately 14,000 MtCO2/y emission [Boot-Handford et al. 2014]. The
technology is currently still in the development stage, but pilot projects are
already in effect, and more are planned over the next decade. Depending
on the literature source the expectation is to capture up to 85-90% of CO2
emissions. Currently, multiple sites are already active or planned within the
EU (Figure 1) and worldwide. To meet climate neutral ambitions, CCS and
CCU efforts will be increased significantly over the next few years.

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 Figure 1. Active/planned CCS projects in Europe

CCS and CCU can be further broken down by the method and placement of the capture technology. Figure 2 is a diagram representing a
summary of the following CCS and CCU applications. Figures 3-5 show these methods in more detail.

Post-Combustion Capture
CO2 can be captured from the flue gas of a combustion process. This can be flue gas coming from any (pressurized) combustion in a boiler,
gas turbine or industrial process yielding CO2. In many cases, the flue gas is first cleaned, with trace components like sulfur dioxide (SO2)
and hydrogen chloride (HCl) being removed to prevent malfunctioning of the capture process. Various capture mechanisms, or combina-
tions of them, can be applied, including phase separation, selective permeability and sorption. The latter mechanism, sorption, is the most
widely utilized mechanism at large point sources. This mechanism encompasses chemical or physical absorption and adsorption. In the CO2
capture processes based on this mechanism, a sorption medium, or a sorbent, is used. When these sorbents are in solution, they are called
solvents. The current research, development and demonstration focus is on using chemical and physical solvents to separate the CO2 from
the gas stream. Retrofitting existing plants with CO2 capture will likely be done with a chemical absorption based post-combustion capture
technology. After CO2 is captured from the flue gas, the inert gases, for example nitrogen (N2), oxygen (O2) and argon (Ar) in the flue gas
are vented to atmosphere. Traces of CO2 will be present in the vented gas due to the efficiency of the capture process being less than 100%.
The research, design and development (RD&D) focus in post-combustion capture is aimed at reducing energy requirement and capital cost
through developing and adapting solvents, optimizing the required process installations and integrating the capture system within the
process. The application of the capture process on contaminated flue gases, for example flue gases from coal fired power plants, is already
commercially applied (Strazisar, Anderson et al. 2003). However, large-scale CO2 capture, as well as dealing with the contaminants in the
flue gas, remains a challenge.

Pre-Combustion Capture
Pre-combustion capture comprises a group of technologies that removes CO2 before the combustion of the fuel. This requires a carbo-
naceous fuel to be broken down into hydrogen (H2) and carbon monoxide (CO), i.e. syngas. To make CO2 capture with high efficiencies
possible, the syngas that is formed after steam reforming or partial oxidation/gasification has to be ‘shifted’ after it is cleaned. The ‘shift re-
action’, or ‘water gas shift’ (WGS) reaction, yields heat and a gas stream with high CO2 and H2 concentrations. The CO2 can then be removed
with chemical and physical solvents, adsorbents and membranes. CO2 traces can be present in the H2 stream.
For the near-term it is expected that chemical or physical solvents (or a combination) are used for the CO2 removal. The CO2 removal step
yields relative pure CO2 and a gas stream with a high H2 and low carbon content. The latter can be used for power production in, for
example, a (modified) gas turbine. The gas with reduced carbon content can, after further purification, also be used in the production of
synfuels, the refining of hydrocarbons, or to produce chemicals (IPCC 2005).
For solid and liquid fuels, pre-combustion CO2 capture can be applied in an IGCC (Integrated Gasification Combined Cycle) power plant. For
gas fired power generation with pre-combustion capture other concepts are being studied (Ertesvag, Kvamsdal et al. 2005; Kvamsdal and
Mejdell 2005; IEA GHG 2006c; Kvamsdal, Jordal et al. 2007).
The technology to capture CO2 from the syngas generated in a gasifier can be considered proven technology, is commercially available and
has been used for several decades in other applications than for electricity production. Examples include H2, NH3 and synthetic fuel produc-
tion (Nexant Inc. 2006). Also, reforming and partial oxidation of (natural) gas are already widely applied, for example in the production of
H2 in the NH3 production process.
The pre-combustion concept has not yet been proven in an IGCC power plant. Proving its reliability and effectiveness in power plant con-
cepts is therefore one of the main RD&D targets. In addition, improving the efficiency of the WGS step and integration of this process with
CO2 capture is also an area of research.
Oxyfuel Combustion
Oxyfuel combustion is based on denitrification of the combustion medium. The nitrogen is removed from the air through a cryogenic air
separation unit (ASU) or with the use of membranes. Combustion thus takes place with nearly pure oxygen. The result is a flue gas contain-
ing mainly CO2 and water. Trace components like oxides of nitrogen (NOx) and SO2 can be present. The CO2 is purified by removing water
and impurities. The remaining small amounts of N2, O2 and Ar are vented off, but can contain traces of CO2. The production of O2 requires
a significant amount of energy, which results in a reduction of the efficiency of the power plant. Further, the purification and the compres-
sion of the CO2 stream also requires energy.
The combustion with O2 is currently applied in the glass and metallurgical industry (Buhre, Elliott et al. 2005; IPCC 2005; M. Anheden,
Jinying Yan et al. 2005). Oxyfuel combustion for steam and power production using solid fuels has been at present only proven in test and
pilot facilities. Oxyfuel combustion can also be applied in natural gas fired concepts. Power cycles for gaseous and solid fuels, however, vary
significantly.
Although there are no significant differences compared to air firing of solid fuels, the combustion process and optimal configuration of the
burners are considered to be the most important hurdles to overcome. In addition, the design and configuration of the flue gas cleaning
section and CO2 purification section are challenges for the short-term. For the gas fired concepts, system integration and development of
critical components hinder direct application on a commercial scale. Examples of critical components are the turbines and combustors for
the near- and medium-term options and, additionally, the fuel reactors for the concepts in the longer term.

Capture from Industrial Process

This group of technologies is often mentioned as the early opportunity for CCS at relative low cost. The total reduction potential due to
CO2 capture from these point sources is, however, considered to be rather limited. Examples for industrial processes include the production
of cement, iron and steel, ethylene (oxide), NH3 and H2. In addition, CO2 can be captured from natural gas sweetening processes and from
refineries (IPCC 2005). The capture processes applied are, in general, the same technologies as already described above.

Figure 2. Schematic of the three main principles of CO2 capture technology

 Figure 3. Post-combustion CCS – measurement points

Figure 4. Pre-combustion CCS – measurement points

Figure 5. Oxyfuel-combustion CCS – measurement points

PROCESS MEASURING POINTS
Figures 3–5 show the position of typical measuring points in the CCS process, excluding the process control points on SMR/power plant the
CO2 is derived from. Tables 1-3 below list the respective gas analysis requirements together with the typical ranges and Servomex analyzers
suited for each measurement. At present, the reported capture efficiency of the above-mentioned capture processes range from 95 to
>99%. This means up to 5% of the CO2 is still vented to the atmosphere at the capture installation, either through direct emission to the
atmosphere or through indirect emissions from degassing of the water from the dehydration step at compression.

Installation location Gas Measured Measuring Range Application Servomex Analyzer

CO2 20%
CO 500/3,000 ppm
NOx 500/3,000 ppm SERVOPRO 4900 Multigas
Flue gas from power plant Emissions
O2 25% SERVOTOUGH SpectraExact 2500
(1)
SO2 100/2,000 ppm
H 2O 30%
SERVOTOUGH SpectraExact 2500
CO2 100% (2)
SERVOPRO DF745SG
CO2 stream capturing/product SO2 100 ppm Quality
SERVOPRO MultiExact 4100 (3)
H 2O 70 ppm
SERVOPRO AquaXact 1688
Lean absorbent stream from SERVOTOUGH SpectraExact 2500
CO2 (slip) 1%/10% Process control
CO2 stripper SERVOPRO MultiExact 4100
CO2 4% (4)
SERVOTOUGH SpectraExact 2500
H 2S 100 ppm
SERVOPRO MultiExact 4100
Pipeline/temporary storage H 2O 70 ppm Safety
SERVOPRO DF-745SG
O2 21%
SERVOPRO AquaXact 1688
NH3 10 ppm
CO2 5% (5)
CO 100/1,000 ppm
Flue gas to stack NOx 500 ppm Emissions SERVOPRO 4900 Multigas
O2 25%
SO2 100/2,000 ppm
SERVOTOUGH Oxy 1900
CO2 4% (4)
CO2 Storage Safety SERVOTOUGH SpectraExact 2500
O2 21%
SERVOPRO MultiExact 4100

(1) To increase efficiency of CO2 absorbent desulfurisation can be used. Range 0-2,000 ppm SO2 at inlet, range 0-100 ppm SO2 at outlet.
(2) Uncertainty <1.5% as per MRG (EU, 2010), Annex I or <2.5% for transferred CO2 from the capture installation MRG (EU, 2010), Annex XVI.
(3) ME4100, DF only if area classified as safe area.
(4) OSHA PEL 0.5% CO2 and permanent damage expected >4%. Storage Directive (EU, 2009), monitoring if CO2 leakage is damaging the environment
or human health. MRG (EU, 2010), Annex XVI, uncertainty <2.5% for transferred CO2 from the capture installation, in the transport network and to the
storage site. Servomex can only offer measurement of decompressed CO2 (gaseous).
(5) CO2 concentration in vented (flue) gases in post-combustion capture processes.

Table 1. Post combustion measurement points

Installation location Gas Measured Measuring Range Application Servomex Analyzer

CO2 5/10%
NOx 500 ppm
Flue gas to stack Emissions SERVOPRO 4900 Multigas
O2 25%
SO2 100/2,000 ppm
CO2 100% (3)
CO2 stream to storage H 2S 1-2% (1) SERVOTOUGH SpectraExact 2500
Quality
(product) CO 300-4,000 ppm (1) SERVOPRO AquaXact 1688
SO2 100 ppm
CO2 4% (2)
SERVOTOUGH SpectraExact 2500
H 2S 100 ppm
Pipeline/temporary storage Safety SERVOPRO MultiExact 4100
H 2O 70 ppm
O2 21%
SERVOTOUGH Oxy 1900
CO2 4% (2)
CO2 Storage Safety SERVOTOUGH SpectraExact 2500
O2 21%
SERVOPRO MultiExact 4100

(1) Pre-combustion carbon capture only.

(2) OSHA PEL 0.5% CO2 and permanent damage expected >4%. Storage Directive (EU, 2009), monitoring if CO2 leakage is damaging the environment
or human health. MRG (EU, 2010), Annex XVI, uncertainty <2.5% for transferred CO2 from the capture installation, in the transport network and to the
storage site. Servomex can only offer measurement of decompressed CO2 (gaseous).
(3) Uncertainty <1.5% as per MRG (EU, 2010), Annex I or <2.5% for transferred CO2 from the capture installation MRG (EU, 2010), Annex XVI.

Table 2. Pre combustion measurement points

Installation location Gas Measured Measuring Range Application Servomex Analyzer
SERVOTOUGH OxyExact 2200
O2 stream (ASU) O2 100% Quality
SERVOPRO MultiExact 4100

CO 1,000 ppm SERVOTOUGH Laser 3 Plus (1),

Combustion control O2 50% Process Control SERVOTOUGH FluegasExact 2700
(modified)

CO2 80%
CO 500/3,000 ppm
Flue gas NOx 500 ppm Process Control SERVOPRO 4900 Multigas
O2 25%
SO2 100/2,000 ppm
CO2 100% (4)
SERVOTOUGH SpectraExact 2500
CO2 stream outlet cooler SO2 100 ppm
Quality SERVOPRO DF-745SGMax
(product) H 2O 70 ppm
SERVOPRO AquaXact 1688
O2 5% (2)
CO2 4% (3)
SERVOTOUGH SpectraExact 2500
H 2S 100 ppm
SERVOPRO MultiExact 4100
Pipeline/temporary storage H 2O 70 ppm Safety
SERVOPRO DF-745SGMax
O2 21%
SERVOPRO AquaXact 1688
NH3 10 ppm
SERVOTOUGH Oxy 1900
CO2 4% (3)
CO2 Storage Safety SERVOTOUGH SpectraExact 2500
O2 21%
SERVOPRO MultiExact 4100

(1) Control of O2 >21% for Oxyfuel combustion is currently not available in-situ Laser 3 Plus.
(2) 3.7-4.1% N2/Ar/O2 in Oxyfuel derived dried CO2
(3) OSHA PEL 0.5% CO2 and permanent damage expected >4%. Storage Directive (EU, 2009), monitoring if CO2 leakage is damaging the environment
or human health. MRG (EU, 2010), Annex XVI, uncertainty <2.5% for transferred CO2 from the capture installation, in the transport network and to the
storage site. Servomex can only offer measurement of decompressed CO2 (gaseous).
(4) Uncertainty <1.5% as per MRG (EU, 2010), Annex I or <2.5% for transferred CO2 from the capture installation MRG (EU, 2010), Annex XVI.

Table 3. Oxyfuel combustion measurement points

APPLICATION Emissions
Incomplete combustion leads to higher carbon monoxide (CO) production, excessive particulate matter or smoke (measured as opacity),
sulfur dioxide (SO2) and oxides of nitrogen (NOx) when excess O2 is present. These gases are detrimental to the environment and are reg-
ulated worldwide but to different levels in each country. Continuous emissions monitoring systems (CEMS) are generally required by most
regulatory bodies as they attempt to rein in pollution emitted from power plants, both public and private. While every region applies their
own rules for how the analyzers must function, which gases and levels must be monitored and how the data needs to be reported, most
need to continuously monitor O2 for reference and the pollutants SO2 and NOx. CO, CO2, and particulate matter (PM) may also be included
depending on local requirements.

SERVOMEX SOLUTION
The 4900 Multigas analyzer is used to analyze SO2, NOx, CO, CO2 and O2 in the stack prior to the flue
4900 Multigas gas emitting to the atmosphere. The 4900 Multigas is a multicomponent extractive analyser that can
measure up to 4 components in a single chassis, so generally only one analyzer is needed for most
CEMS gas analysis requirements. The analyzer requires a clean dry sample hence, a sample conditioning
system is required which can be supplied by Servomex. The CEMS system typically consists of a sample
probe, heated filter unit, heated sample line, pump and chiller with the sample flow control to match
each analyser’s requirement. If NOx is required, a NOx converter can be supplied which converts the
nitrogen dioxide (NO2) in the flue gas to nitric oxide (NO), thus enabling the 4900 Multigas to measure
total NOx. Other components can also be added to the Servomex CEMS system package as required,
such as flow monitors, dust monitors, and data loggers. The data logger is required to log and report
the CEMS analysis in accordance with the local legislative requirements.

APPLICATION Quality
Because captured CO2 is a useful product for the manufacturing of fuels, carbonates, polymers and other chemicals, its quality post capture
requires close monitoring. If captured from a process such as coal-fired power generation, the captured CO2 can contain traces of contami-
nants like sulfur dioxide (SO2) and hydrogen sulfide (H2S).
The measurement is made after CO2 is captured in the stack, or after the methyl diethanolamine (MDEA) outlet, pre-transport to the CO2 user.

SERVOMEX SOLUTION
SpectraExact 2500 The SpectraExact 2500, in combination with a back pressure regulator, offers an accuracy of +/-0.2%
between the range of 80-100% CO2. Depending on the required accuracy, impurities of CO and SO2
and, depending on range, H2O could be offered.
Trace CO2 and O2 is available in the MultiExact 4100, with trace SO2 currently offered in the 4900
Multigas.
For both the SpectraExact 2500 and MultiExact 4100 / 4900 Multigas, it will be necessary to compensate
for any CO2 in the background. Trace O2 and lower traces of H2O can also be offered with the SERVOPRO
MonoExact DF310E and SERVOPRO DF-700 Series. Note, the DF series, as well as the 4000 series, can cur-
rently only be installed in safe area. All mentioned analyzers require a suitable sampling system which
conditions the sample to analyzer requirements.
MultiExact 4100

MonoExact DF310E
APPLICATION Safety
Monitoring traces of H2S and H2O in pipelines is required to avoid sweet and sour corrosion. Further, monitoring of CO2 and O2 in ambient
air for safety of personnel in enclosed spaces around the pipeline/storage and to detect leakage is required.

SERVOMEX SOLUTION
DF-745SGMax Currently, Servomex can offer a safe area solution for trace H2O measurement in CO2 with the
DF-745SGMax. The trace level tuneable diode laser (TDL) provides high stability measurements through
minimal moisture contact with optical elements. Detection range of 0-100 ppm with an accuracy +/-5%
of reading or +/-5 ppb (whichever is greater). Factory calibrated, the zero-drift performance delivered
by the high stability TDL requires no ongoing calibration, while the non-depleting sensor technology
never needs replacing. In closed environments which allow sampling, the Oxy 1900 (paramagnetic) for
O2 and SpectraExact 2500 (infrared) for CO2 can be used for hazardous area installation. The SpectraEx-
act 2500 offers an accuracy of +/-1%of the scale for the measurement of CO2. The Oxy 1900 offers a
measurement range of 0-25% O2 with an accuracy of +/-0.05% O2 or better.
In closed environments which allow sampling and are rated as general-purpose area, the MultiExact
4100 can be used for O2 and CO2 measurement. Suitable sampling systems which condition the sample
to analyzer requirements are needed. The measurement ranges for monitoring CO2 storage/network
for leakage should be selected in compliance with OSHA recommendation considering damage to
environment or human health.

APPLICATION Combustion Control (Oxyfuel)

The oxyfuel reaction relies on the oxidation of fuel with near pure O2 rather than the traditional combustion air. The use of pure O2 means
no N2 is introduced to the process to form NOx, and thus this is a good strategy for reducing emissions, aside from the fact it can be expen-
sive and more of a safety hazard. Fuel and O2 are fed into the boiler/furnace/heater where combustion takes place as normal. Because the
combustion process is not perfect, excess O2 is required to ensure that there is complete combustion, however, too much will reduce the
combustion efficiency due to increased heat loss to the atmosphere. Conversely if there is too little O2 the combustion efficiency will fall
dramatically since the fuel is not being completely burnt and not all the energy is being released. This will also result in an even greater
environmental impact as CO and other hydrocarbons will also be emitted, thus the importance for optimization of the excess air at the
minimum level required for complete combustion, ensuring that combustion efficiency is optimized and emissions are minimized. Due to
changes in output demand, aging equipment, varying fuel composition, atmospheric conditions and process conditions, this optimum oper-
ating point varies. By continuously monitoring the amount of oxygen and combustibles in the flue gas, prompt adjustments can be made to
the boiler control system to maintain peak efficiency.

SERVOMEX SOLUTION
FluegasExact 2700 Traditional zirconia technology cannot often be utilized for oxyfuel excess O2 measurement, as the
technology can typically only measure up to 21% O2. This is due to the fundamentals of how the tech-
nology operates (with the reference side of the zirconia being exposed to ambient air containing 21%
O2. When the sample side and reference side are equal at 21% O2, the sensor output is zero).
The SERVOTOUGH FluegasExact 2700 flue gas analyzer, however, can be modified using special soft-
ware to operate at a range of 0-50% O2, even with the zirconia reference being exposed to ambient
air. There is little to no detriment to analyzer performance and safety concerns are addressed by the
analyzers integral and standard flame traps that protect all routes back to process.
The FluegasExact 2700 can monitor both O2 and combustibles (COe). O2 is measured using zirconium
oxide sensor technology. A thick film catalytic sensor optimized for CO is used to detect ppm levels of
combustibles and monitor breakthrough, the point the process runs out of O2 available to fully burn
the fuel, thus producing high levels of CO. To enable preventative maintenance, an optional flow sen-
sor is available that monitors the flow up the analyzer’s probe and through the sensors. These sensors
are housed in a sensor head mounted on the process wall to which a sample is aspirated via a sample
probe.
 WE’RE READY TO HELP
WHATEVER YOUR GAS ANALYSIS REQUIREMENTS, WHEREVER YOU ARE
AN111 Rev.2 Date: 10/21

These analyzers are not intended for any form of use on humans and are not medical devices as described in the Medical Devices Directive 93/42EEC.

Please note: Whilst every effort has been made to ensure accuracy, no responsibility can be accepted for errors and omissions.
Data may change, as well as legislation, and you are strongly advised to obtain copies of the most recently issued regulations, standards and guidelines.
This document is not intended to form the basis of a contract.

Servomex has a policy of constant product improvement and reserves the right to change specifications without notice. © Servomex Group Limited. 2021.
A Spectris company. All rights reserved.

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