International Journal of Greenhouse Gas Control 113 (2022) 103513

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International Journal of Greenhouse Gas Control

journal homepage: www.elsevier.com/locate/ijggc

Development and testing of a new post-combustion CO2 capture solvent in

pilot and demonstration plant
Lianbo Liu a, b, Mengxiang Fang a, *, Shisen Xu b, Jinyi Wang b, Dongfang Guo b
a
State Key Laboratory of Clean Energy Utilization (Zhejiang University), Hangzhou 310027, Zhejiang Province, China
b
Beijing Key Laboratory of CO2 Capture and Process(China Huaneng Group Clean Energy Research Institute), Changping District, Beijing 102209, China

A R T I C L E I N F O A B S T R A C T

Key words: Post-combustion CO2 capture for coal-fired power plants is an important technical option to mitigate greenhouse
CO2 capture gas emission from coal-based power generation. CO2 capture based on chemical absorption is currently the
Coal-fired flue gas dominant technology for large-scale capture unit. The main obstacle of commercial application is the high cost
Regeneration heat consumption
and high energy consumption, innovation of new absorption solvent is one of the keys to the performance
Capture ratio
Absorption solvent
improvement. Based on the characteristics of flue gas, combined with the analysis and comparison of potential
True heat flux amine components, the formula of blended amines are developed, which is further screened by true-heat flux
Reaction heat calorimetric test combined with vapor-liquid equilibrium test, HNC-5 is selected through the lab test, because of
Alkanolamine its lower heat of absorption and higher capture performance. The test on a 1000 t/a CO2 capture pilot plant
under real flue gas conditions shows that the performance index of HNC-5 is consistent with the lab test results.
The CO2 capture ratio is higher than 90%, and the heat consumption during regeneration is reduced by about
20% compared with MEA. The continuous operation results of the 120,000-ton/year CO2 capture unit show that
heat duty of regeneration of HNC-5 is about 2.8GJ/tCO2, the cost per ton of CO2 captured is reduced by about 63
CNY, the usage life is longer, helping improve the system availability and reliability.

1. Introduction The power system is characterized by concentrated emission sources

and high CO2 emission intensity. For example, in 2019 (Liu et al., 2018),
The climate change poses a major challenge to sustainable devel­ the CO2 emissions from the power system in China are about 3.8 Gt,
opment of human society. One of the most important tasks for accounting for 38% of the total carbon emissions generated from the
addressing the climate change is to substantially and continuously energy utilization process around the country. Capturing CO2 generated
reduce the emission of greenhouse gas carbon dioxide (IPCC Climate from power plants is one of the most effective ways to achieve carbon
Change, 2014). Carbon capture, utilization and storage (CCUS) tech­ emission reduction. Three methods are available for capturing CO2 in
nology is one of the options with potential of reducing emission signif­ power systems: post-combustion capture, pre-combustion capture and
icantly. The relevant research of the International Energy Agency (IEA) oxy-fuel combustion (Metz et al., 2005). The flue gas emitted from the
has shown that (Agency International Energy, 2016), CCUS technology existing power plants is mainly treated using post-combustion capture
must be adopted for achieving the goal of controlling the average tem­ method based on chemical absorption technology. As the CO2 gas
perature rise around the globe within 2◦ C compared with the source, flue gas emitted from coal-fired power plants is featured with
pre-industrial level because its emission reduction contribution rate large volumetric flow, low CO2 partial pressure (<15kPa), and complex
ranges from 10% to 20%, and it is the main way to achieve direct composition (including H2O, O2, SOx, NOx, particulate matters) (Xu and
emission reduction against the backdrop that the marginal emission Gao, 2009). Generally, in the chemical absorption method, alkaline
reduction contributed by renewable energy substitution and energy ef­ absorbent reacts with the acid gas CO2 to separate CO2 from the gas
ficiency improvement tends to decline with time. China’s coal-based phase. The chemical reaction occurs at a large rate. As compared with
energy structure will sustain for a long time and, therefore, CCUS adsorption method, membrane separation method, the chemical ab­
technology is essential for the sustainable utilization of coal-based en­ sorption method can achieve quick absorption of CO2 and larger ab­
ergy in the future. sorption capacity even under low CO2 partial pressure condition,

* Corresponding author at:Zhejiang University, China.

E-mail address: [email protected] (M. Fang).

https://doi.org/10.1016/j.ijggc.2021.103513
Received 24 December 2020; Received in revised form 28 July 2021; Accepted 17 October 2021
Available online 16 December 2021
1750-5836/© 2021 Published by Elsevier Ltd.
L. Liu et al. International Journal of Greenhouse Gas Control 113 (2022) 103513

making it possible for utilizing a small-capacity equipment to treat a continuous loss of active ingredients in the absorption solution. Most
large amount of flue gas. The chemical absorption method has been organic absorbents will react with the oxygen in the flue gas, causing
widely used in power plant CO2 capture projects. Based on this process, irreversible oxidative degradation or oxidative degradation at high
coal-fired power plants in Canada and the United States have imple­ temperatures. The degradation of absorbent is an important reason for
mented pilot projects with a CO2 capture scale of one million tons/year the loss of absorbent. In addition, some degradation products are highly
(Preston et al., 2018, Mantripragada Hari et al., 2019). corrosive to the equipment, which not only increases maintenance costs,
A typical chemical absorption process is shown in Fig. 1. As shown in but also affects the reliability of the equipment. The above degradation
the Fig., the flue gas enters the absorption tower after cooling, and and corrosion will lead to increased operating costs. Therefore, how to
contacts the alkaline absorbent lean solution in counter flow. Through a reduce the energy consumption and cost of CO2 capture technology is a
series of processes including mass transfer, diffusion and reaction, CO2 major challenge for the development of this technology, and the solution
becomes unstable compounds that are dissolvable in water under the hinges on the development of new high-efficiency and low-energy
effect of the absorbent. The resulting rich solution flows into the absorbents.
regeneration tower and exchanges heat with high-temperature steam. As
a result, the unstable compounds are heated and decomposed, which is a 2. Alcohol amine-based chemical absorption method
reverse reaction of CO2 absorption reaction. This desorption process
produces regeneration gas which contains CO2 and steam. Through the The commonly used chemical absorbents include alcohol amines,
subsequent cooling and purification, CO2 with a high purity can be ammonia, amino acid salts, carbonates, etc. (Yang et al., 2014, Guo
obtained, and the regeneration of absorbent performance can be et al., 2013, Xi et al., 2012, Rochelle Gary, 2009, Jockenhoevel et al.,
achieved. 2009). New types of absorbents include phase-changing absorbents,
The entire process draws on the difference of the CO2-absorbent- ionic liquid, nanofluids, etc. (Fang et al., 2015, Xu and Wang, 2018,
water reaction balance at different temperatures, which is a function of Huang et al., 2017, Yu et al., 2019). At present, the absorbents used in
the difference in the CO2 absorption capacity of the absorbent at engineering applications mainly include blended amine absorbent
different temperatures. Although the balance of the CO2 chemical ab­ dominated by organic alcohol amines, and composite absorbents con­
sorption/regeneration process is theoretically reversible, additional taining organic alcohol amines. Monoethanolamine (MEA) is represen­
energy is required to overcome the energy barrier of the regeneration tative of alcohol amine. As one type of organic molecule, its functional
reaction, thereby inducing the reaction to occur. In addition, energy is group is characterized in that it contains amino and hydroxyl groups.
required to maintain the reaction rate. The absorbent regeneration The amino group can be dissociated as basic centers and react with CO2;
process consumes the largest amount of heat in the CO2 capture cycle, hydroxyl group can contribute to increased solubility of molecules in
mainly involving reaction enthalpy in dissociation of the intermediate water. In terms of the number of hydrogen atoms around the amino
compounds, the sensible heat of the absorption solution during the nitrogen atom, alcohol amines can be classified into:
heating process, and the latent heat of water vaporization. Although a Primary amine (2 hydrogen atoms), such as MEA;
portion of the heat can be recovered through the optimization of the Secondary amine (1 hydrogen atom), such as diethanolamine (DEA),
heat recovery and regeneration device, most amount of the heat is diisopropylamine (DIPA);
difficult to be reused due to heat dissipation of the equipment and Tertiary amines (no hydrogen atoms), such as triethanolamine
pipelines and deteriorated quality of the heat recovered in the cooling (TEA), N-methyldiethanolamine (MDEA).
process of the regenerated gas. During operation, acid gases, such as SO2 The difference of the substituent group on the amino nitrogen atom
and NOx, contained in the flue gas will first react with alkaline absor­ can cause changes in the dissociation characteristics of the amino group,
bents, and the resulting products cannot be regenerated at the operating which not only affects the absorption reaction path, but also the reaction
temperature of the CO2 regeneration tower. Such reaction products are thermodynamics and kinetic parameters. In terms of reaction mecha­
called heat stable salts which accumulate continuously, resulting in nism, there are two main pathways for absorption reaction (Conway

Purified gas Regenerative Crude CO 2 gas

emission gas cooler
Replenishing
adsorbent Solution
Scrubbing solution purification Regenerative
device gas separator
Lean
solution
cooler

Absorpt
ion Regeneration
Pretreatment tower Filter tower
tower
LP steam
Flue gas
Lean/rich
solution heat
exchanger Reboiler
Induced draft fan
Steam condensate

Fig. 1. Diagram of CO2 chemical absorption process.

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L. Liu et al. International Journal of Greenhouse Gas Control 113 (2022) 103513

et al., 2013): (i) carbamate pathway; (ii) bicarbonate pathway. The re­ In view of the important role of CO2 absorbents in improving the
action speed of pathway (i) is much higher than that of pathway (ii). The performance of CO2 capture technology, the heat flux method and
absorption reaction of primary and secondary amines takes pathway (i) thermodynamic equilibrium integrated reactor are used in this paper to
as the main reaction and proceeds at a stoichiometric ratio of 2:1. As the carry out comprehensive performance test of compound mixed amine
hydrogen atoms on the tertiary amine amino are completely substituted absorbents, in order to screen out new type of absorbent with desirable
by the substituent group and cannot be directly hydrolyzed to produce performance, and demonstrate such performance through pilot test.
protons, only pathway (ii) is possible. Although the stoichiometric ratio Further, the new type of absorbent has been used in engineering appli­
of pathway (ii) is 1:1 and theoretically the absorption capacity per mole cations to verify its long-term performance and economy.
is larger, the reaction rate in pathway (ii) is too low under normal
pressure and is of no significance in industrial application. As a result, 3. Performance analysis in laboratory
accelerators are required. By changing the geometric characteristics of
the molecule, the reaction can be deviated towards pathway (ii) with Planar molecules with desirable structural rigidity are selected based
lower energy consumption. For example, introducing a sterically hin­ on absorption capacity, cycle capacity, reaction rate, molecular stability,
dered substituent group on the carbon atom adjacent to the amino group volatility, viscosity and other parameters of alcohol amine monomer.
to form a hindered amine can reduce the probability of amino group They are combined and compounded with tertiary amines, sterically
coming contact with CO2 molecules, thereby facilitating the progress of hindered amine s and accelerator molecules to form four kinds of
reaction pathway (ii). alternative combinations. Each of the combinations comprises 3-4 kinds
In respect of the relationship between the reaction kinetic parame­ of alcohol amine monomers, supplemented by carbonate for adjustment
ters and the geometric characteristics of the alcohol amine molecule, purpose. A real heat flux reaction calorimeter is employed to test the
studies have found that the dissociation constant pKa of the alcohol four combinations for absorption reaction air-liquid equilibrium curve
amine molecule in water is proportional to the reaction rate (Nitta et al., and reaction enthalpy. And the test results are compared with the
2014, Joback Kevin and Heberle, 2017). pKa is an equilibrium constant relevant parameters of MEA.
that characterizes the alcohol amine molecule’s ability of ionizing
hydrogen ions. Given the similar mass transfer rate, the greater the pKa, 3.1. Real heat flux reaction calorimeter
the stronger the alkalinity and the faster the absorption reaction rate.
Primary amine, secondary amine and tertiary amine are in descending The CPA201 real heat flux reaction calorimeter manufactured by
order in terms of pKa, reaction speed. The application of primary amine ChemiSens is employed. The components of the calorimeter are as
and secondary amine is beneficial to shorten the reaction time and even shown in Fig. 2, mainly comprising reactor, thermostat, air/liquid
small equipment can achieve the expected capture scale. However, in inflow controller, temperature and pressure sensor, control unit and
this case, the enthalpy of formation of the intermediate compound is human-computer interaction interface. The reactor is the component
higher, and the regeneration reaction requires higher temperature and where the reaction occurs and is the core unit for parameter measure­
more heat. ment. It is immersed in the constant temperature medium in the ther­
The selection of absorbent also needs to take account of the impact of mostat. The structural schematic diagram of the reactor is shown in
absorbent viscosity and surface tension on gas-liquid mass transfer. Fig. 3. The top cover and base of the reactor are made of 316L stainless
Reduced surface vapor pressure of absorbent can avoid absorbent loss steel, and the top cover is provided with a sensor and a stirring device
and secondary emission of pollutant components caused by absorbent which can record the temperature and pressure of the gas phase medium
volatilization and reduced corrosion of the absorbent on the capture inside the reactor. The reactor wall is in form of a double-layer glass
device (Kittel and Gonzalez, 2014) can reduce the operating cost of the jacket which provides a thermal insulation layer. The heat transfer be­
equipment and improve the reliability of the system. Moreover, the tween the reactor and the external constant temperature environment
selected absorbent shall have stable chemical property, and can be only occurs through the base. The base is provided with a thermocouple
resistant to gas impurities, especially oxygen side reactions, and reduce to measure the temperature of the liquid. The Peltier element in the base
the degradation loss of absorbent (Liu et al., 2014). In practical appli­ receives the signal from the control unit to heat or cool the medium,
cations, the raw materials of the selected absorbent shall be available allowing the liquid temperature inside the reactor to reach the set
from a great variety of sources and enjoy lower costs, facilitating the temperature. Inside the reactor, a heat flow sensor is provided on the
large-scale promotion of the absorbent. In summary, it is necessary to heat transfer path between the liquid and the Peltier element to record
carry out comprehensive design of the physical and chemical properties the heat flux value of the heat transfer process in real time.
of absorbent molecules in order to improve the overall performance of The main technical indicators of the calorimeter are as follows:
absorbents through trade-off and combinations of various factors. constant-temperature heating bath capacity 13L, reactor capacity 250
In the development of absorbents, new molecules can be designed mL, liquid measurement volume: 10~180mL; reactor test pressure
and developed based on the structure-activity relationship between the range: from vacuum to 2MPa; test temperature range: -10℃ to 160℃;
structure and chemical properties of a single molecule. On this basis, test modes: constant temperature, temperature scanning, constant heat
several types of absorbents can be blended to comprehensively utilize flux, variable temperature, ambient constant temperature; heat detec­
the characteristics of different absorbent components, thus obtaining a tion limit: 5J; power resolution: 0.03W. It can be used to accurately
combination of absorbents with the highest overall efficiency of the measure the heat change in the reaction system. The reactor has been
absorption/desorption cycle and the lowest energy consumption for CO2 subjected to calorimetric check within its test temperature range before
capture. This is also a commonly used strategy in the development of the experiment.
absorbents. In the previous research on evaluating the performance of
mixed amine absorbents, the researchers mostly focus on the measure­ 3.2. Test method with calorimeter
ment of vapor-liquid equilibrium (VLE) and reaction rate. Some studies
focus on the enthalpy of CO2 absorption/regeneration. As the mea­ During the CO2 absorption reaction measurement process, add about
surement of reaction enthalpy is affected by the blending method, 100 mL of absorbent solution into the reactor, and immerse the reactor
measuring principle and equipment difference, the reported reaction into a constant temperature medium (propylene glycol). When the
enthalpy values vary greatly. Moreover, there is also a lack of measuring reactor reaches a constant temperature, that is, the solution temperature
devices and methods that combine thermodynamics, kinetics, and re­ reaches the set value and maintains at it for 200 seconds, while the heat
action enthalpy. This results in a certain deviation in the comprehensive flux change is less than 0.05W, inject CO2 into the reactor at fixed flow
evaluation of absorbent performance. and in batches. In the experiment, the control steps of the injecting gas in

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L. Liu et al. International Journal of Greenhouse Gas Control 113 (2022) 103513

Fig. 2. Diagram of reaction calorimeter apparatus.

Fig. 3. Diagram of calorimeter reactor (arrow indicating the heat transfer direction).

batches are as follows: method of absorption enthalpy are detailed in reference (Xu et al., 2015,
Guo et al., 2016).
Step 1: Set the temperature to 40◦ C, and heat up the reactor and the
constant-temperature heating bath at the same time;
Step 2: Once the reactor reaches the above constant temperature, 3.3. Test results
open the CO2 inlet valve to control the inflow rate, and close the inlet
valve when the single inflow amount reaches the preset value; The performance test of absorbent is based on the MEA solution.
Step 3: Wait for the reactor to reach the constant temperature again, Fig. 4 shows the change of absorption enthalpy of MEA solution (30% by
indicating that the single inlet gas reaction has reached equilibrium; weight) loaded with CO2 and CO2 partial pressure in the gas phase as a
Step 4: Return to Step 2 to repeat the cycle, until the total mass of function of CO2 molar load of the absorbent at 40℃. In the figure, the
inlet CO2 reaches the set value or the gas pressure inside the reactor differential enthalpy (ΔHdiff) is defined as the ratio of the heat released
reaches the set value; by the absorption reaction after a single CO2 inlet to the amount of CO2
added at a time, kJ/mol; the integral enthalpy (ΔHint) is defined as the
Some original data obtained directly during the experiment is shown ratio of the total amount of heat released by the reaction system starting
in Fig. 4 (only two dosing cycles are shown here). from the initial CO2 inlet to the total amount of CO2 absorption, kJ/mol.
The measurement method of real heat flux and the calculation Conventionally, reaction enthalpy is measured by adding CO2 into the
solution continuously until the saturation condition is achieved, and

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L. Liu et al. International Journal of Greenhouse Gas Control 113 (2022) 103513

Fig. 4. VLE and reaction heat diagram of absorption reaction between 30% by weight MEA and CO2 at 40℃.

then calculating the average absorption enthalpy based on the total Figs. 5–8 show the change of absorption enthalpy of four alternative
amount. Thus, the integral enthalpy is obtained. Repeat the measure­ mixed amine solutions (30% by weight) and CO2 partial pressure in the
ment for at least twice, and the data deviation shall be within 5%. gas phase as a function of CO2 molar load of the absorbent at 40℃.
At a molar load smaller than 0.5, MEA absorbent (30% by weight) In industrial applications, the CO2 molar load of alcohol amine
has a differential absorption enthalpy, ΔHdiff, of about 100 kJ/mol, absorbent is obtained through simulation and operation optimization.
which is close to the theoretical calculation value (Gupta et al., 2013), On the one hand, it is necessary to increase the difference of molar load
and slightly higher than the values measured by calorimeters in the between rich solution and lean solution, namely, to increase the capacity
previous literature, 80-95 kJ/mol (Kim and Svendsen Hallvard, 2007, of the absorption/regeneration cycle; and on the other hand, it is also
Kim et al., 2009). The gas inlet rate, gas phase pressure in the absorption necessary to control the regeneration temperature and time and hence
reaction, reaction temperature, pre-calibrated value of the heat flux the heat consumption of regeneration. Generally, the CO2 load of rich
sensor, etc., all have an impact on the measured value of the absorption solution is 0.5-0.6; that of lean solution is 0.2-0.3. Therefore, the use of
enthalpy. Therefore, with the same instrument, condition and operation absorbents with a smaller reaction enthalpy for CO2 load less than 0.6 is
method, the difference of absorption enthalpy between different ab­ more conducive to reducing heat consumption. Through comparison, it
sorbents can be obtained in a unified system, thereby measuring the follows that, among the four formulas above, Formula 4 has the lowest
regeneration enthalpy of the regeneration reaction. absorption enthalpy, which is more than 20% lower than that of MEA.

Fig. 5. VLE and reaction heat diagram of absorption reaction between Formula-1 (30% by weight) solvent and CO2 at 40℃.

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L. Liu et al. International Journal of Greenhouse Gas Control 113 (2022) 103513

Fig. 6. VLE and reaction heat diagram of absorption reaction between Formula-2 (30% by weight) solvent and CO2 at 40℃.

Fig. 7. VLE and reaction heat diagram of absorption reaction between Formula-3 (30% by weight) solvent and CO2 at 40℃.

As such, Formula 4 is superior to MEA in terms of both reaction rate and Huaneng Changchun Thermal Power Plant was performed, plant photo
reaction enthalpy. The further physical parameter measurement shows see Fig. 9. The test result has been compared with the previous basic
that the viscosity of Formula 4 is comparable to that of MEA, and the performance test of MEA solution as well as the laboratory test data.
absorbent phase is stable during the reaction process. Therefore, For­ The structure of the pilot plant and the basic operation test of MEA
mula 4 is selected as the preferred component to carry out subsequent are detailed in references (Wang et al., 2015; Feron et al., 2017). The
scale-up test and demonstration, and it is named with HNC-5. feedstock gas of the pilot plant is draw from the scrubbed flue gas
through FGD (Flue Gas Desulfurization). A flue gas pretreatment unit is
4. Pilot test installed in front of the absorption tower to control the inlet gas tem­
perature and acid gas composition. The design flow of inlet gas is
4.1. Pilot test plant 500Nm3/h, the design capture capacity is 100~125 kg/h, the design
specific surface area of the packing is 250m2/m3, the design absorption
In order to verify the capture performance of the novel absorbent temperature is 40~60℃, and the design regeneration temperature is
HNC-5 under the real flue gas conditions of coal-fired power plants, an 115-125℃.
operational test of 1,000-ton/year CO2 capture pilot test plant of

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L. Liu et al. International Journal of Greenhouse Gas Control 113 (2022) 103513

Fig. 8. VLE and reaction heat diagram of absorption reaction between Formula-4 (30% by weight) solvent and CO2 at 40℃.

rate, it is found that the heat load of the reboiler during operation,
namely, the heat consumption for regeneration of HNC-5 in producing
per unit of CO2, is about 3.0GJ/tCO2. The uncertainty of the data result
is about 5%, see Fig. 11.
In the previous benchmark performance test of MEA solution under
the same conditions of the plant, when the liquid-to-gas ratio of the MEA
lean solution to the flue gas in the absorption tower is 4.0, the energy
consumption of the system during optimized operating condition is the
lowest, and the MEA regeneration heat consumption is 3.6GJ/tCO2.
Fig. 12 reflects the change of the gas pressure in the reactor, while inject
the same amount of carbon dioxide into the 30wt.% MEA and 30wt.%
HNC-5 solution system of the same quality respectively. The curve
shows that HNC-5 absorbent has a faster absorption reaction rate than
MEA, therefore, the system can operate at a lower liquid-to-gas ratio,
while maintaining the specified CO2 capture rate and CO2 yield. At 90%
capture rate, the regeneration heat consumption of HNC-5 absorbent for
CO2 capture is about 20% lower than that of MEA, which is basically
consistent with the experimental measurement.

5. Engineering application

5.1. Capture system

Fig. 9. Photo of 1000t/a CO2 capture pilot plant in Changchun Thermal

After the pilot performance test is completed, HNC-5 absorbent was
Power Plant.
officially used in the industrial capture plant: 120,000 tons/year CO2
capture system of Huaneng Shanghai Shidongkou Second Power Plant. It
4.2. Pilot test results
is constructed as a supporting project for Shidongkou Second Power
Plant Phase II 2x660MW domestic ultra-supercritical units. With a
The main operating parameters during the performance test of HNC-
design flow of 66000Nm3/h, it comprises a capture area and a refining
5 absorbent are as follows: the flue gas flow at the inlet of the absorption
area, and can produce food-grade purity CO2 products. It was completed
tower is maintained at about 450Nm3/h, and the volume fraction of CO2
in 2009. Afterwards, the system has been subjected to development and
in the flue gas is maintained in the range of 11.0-11.5%, as shown in
demonstration of several new technologies, including flue gas pre­
Fig. 10.
treatment, waste liquid disposal, new types of equipment as well as
Through operation optimization, the HNC-5 aqueous solution (lean
system anti-corrosion. After renovation, it has an operating time of more
solution) with a mass fraction of 25% was added from the top of the
than 2000h per year since 2015, making it the largest post-combustion
absorption tower to react with the flue gas at a liquid-to-gas ratio of 2.5.
CO2 capture device with the longest cumulative operating time in China
The volume fraction of CO2 in the flue gas at the outlet of the absorption
today (Wang and Xu, 2014).
tower is reduced to about 1.0%. The capture rate of the absorption plant
for CO2 in the flue gas is maintained above 90%. The operating tem­
perature of the reboiler at the bottom of the regeneration tower is
maintained at about 110◦ C. Through calculating the steam consumption

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L. Liu et al. International Journal of Greenhouse Gas Control 113 (2022) 103513

Fig. 10. Flue gas parameters during pilot test of HNC-5.

Fig. 11. Capture performance of HNC-5 during pilot test.

5.2. Test results the cost of steam per GJ is CNY 60, the operating cost can be reduced by
CNY 37.8 due to the reduction of steam consumption. As such, the total
In the demonstration operation of HNC-5 absorbent, the initial production cost per ton of CO2 by the system is reduced by CNY 62.82
concentration comparable to the previous MEA-based absorbent oper­ when HNC-5 absorbent is used. The absorbent regeneration heat con­
ation is adopted, with a mass fraction of 25%-30%. The comparative test sumption measured on the demonstration plant is even lower because
is mainly intended to investigate the tolerance and reliability of the that the heat dissipation of the packed tower and pipeline is relatively
absorption solvent under actual industrial flue gas conditions and obtain less due to increased size of the capture equipment, which is more
the loss data of the absorbent in the long-term operation of the conducive to reducing the energy consumption for capturing each ton of
industrial-scale plant, and to measure the regeneration heat consump­ CO2.
tion based on the steam consumption rate. Table 1 summarizes the During the demonstration operation, the HNC-5 absorbent exhibited
typical comprehensive performance data and economic indicators of desirable stability and reliability, which mainly lies in that the loss of the
HNC-5 absorbent and MEA-based absorbent. absorbent is significantly less than that of MEA, see Fig. 13. During the
It follows from the above table that, when HNC-5 absorbent is used, test, the mass fraction of MEA in the lean solution was reduced from
the cost of raw material consumption per ton of CO2 produced by the 25.13% to 13.46%, and its concentration was reduced by about 46.44%,
capture system is reduced by CNY 25.02, a decrease of 29.6%; the steam which is attributable to the entrainment of liquid droplets by the flue
consumption is reduced by 0.63GJ, a decrease of 18.4%. Assuming that gas, the evaporation of MEA itself and the degradation loss. As a chain-

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L. Liu et al. International Journal of Greenhouse Gas Control 113 (2022) 103513

Fig. 12. Partial pressure change curve of carbon dioxide after absorption reaction with MEA and HNC-5.

shaped small molecule, MEA is prone to oxidative degradation and

Table 1
polymerization reactions. The test on composition of the absorbent also
Operation performance index and capture cost using MEA and HNC-5 absorption
reveals the rapid accumulation of formate, acetate, and oxalate over
solvent.
time, indicating continuous degradation of MEA during operation.
Item Unit MEA HNC-5 Under the same operating conditions, the mass fraction of the active
Absorbent consumption kg/tCO2 4.69 1.32 ingredients of HNC-5 absorbent is maintained at a concentration range
Unit price of raw material CNY/kg 18 45 of 25%-21% for a long time (over 500h), and the accumulation rate of
Cost of absorbent raw material CNY/tCO2 84.42 59.4
degradation products is only 10%-20% of MEA. This shows that the
Steam consumption GJ/tCO2 3.43 2.8
Heat consumption cost CNY/GJ 60 60 stability of the chemical structure of absorbent can increase the service
Steam cost in operation CNY/tCO2 205.8 168 life of the absorbent, thereby improving the availability and reliability of
the capture system.

Fig. 13. Solvent concentration (by weight) loss of MEA and HNC-5 during demonstration operation.

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6. Conclusions Guo, D., Gao, S., Luo, W., et al., 2016. Effect of sulfolane on CO2 absorption and
desorption by monoethanolamine aqueous solution. CIESC Journal (12), 5244–5251.
Guo, D., Wang, J., Gabrielda, S., et al., 2013. Reactivity and mechanism study of CO2
The post-combustion capture technology based on chemical ab­ with amino acids as carbon capture solvents. In: Proceedings of the CSEE, pp. 29–33.
sorption method is an important technical option for CO2 emission Gupta, M., Da Silva Eirik, F., Hartono, A., et al., 2013. Theoretical study of differential
reduction in coal-fired power plants. To overcome the disadvantages of enthalpy of absorption of CO2 with MEA and MDEA as a function of temperature.
The Journal of Physical Chemistry B 117 (32), 9457–9468.
high capture cost and high energy consumption of this technology, it is Huang, Y., Cui, G., Zhao, Y., et al., 2017. Preorganization and cooperation for highly
necessary to improve its overall performance through innovation of efficient and reversible capture of low-concentration CO2 by ionic liquids.
absorbents. Based on the analysis of the alcohol amine absorbent Angewandte Chemie International Edition 56 (43), 13293–13297.
IPCC Climate Change, 2014. Mitigation of climate change. Contribution of Working
monomer, this study has optimized four compound mixed amine Group III to the Fifth Assessment Report of the Intergovernmental Panel on Climate
absorbent combinations. Through comparison test with MEA as the Change. Cambridge University Press, Cambridge.
reference and heat flux calorimeter, it is found that Formula 4 enjoys Joback Kevin, G., Heberle, J.R., Bhown Abhoyjit, S, 2017. Influence of pKa and amine
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