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Journal of Cleaner Production

Volume ���, �� December ����, ������

An environment-friendly process for limestone calcination

with CO2 looping and recovery
Binfan Jiang a, Dehong Xia a b , Bo Yu a, Rui Xiong a, Wenqing Ao a, Peikun Zhang a b, Lin Cong c

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Abstract

Lime production represents the second largest contributor to industrial CO2 emission in China, but it has not been well
addressed. Herein, an efficient and environment-friendly Limestone Calcination Process with CO2 Looping and Recovery
(LCPCLR) is established to solve the associated environment issue. CO2 serves as heat carrier in the LCPCLR system,
which provides heat for the limestone calcination. The limestone calcination occurs in pure CO2 environment, and the
calcination temperature is around 900 °C when CO2 pressure (PCO2) is at ∼1 atm. CaCO3 decomposition is inhibited
when PCO2 exceeds the CO2 equilibrium pressure (PCO2eq), and the inhibition can be solved by increase of temperature.
PCO2/PCO2eq is suggested to be kept below 0.25 to achieve an efficient calcination process. Both higher temperature and
larger gas-solid water equivalent ratio (ηg/s) can enhance the limestone calcination. To replace the pure CO2 with
CO2/H2O(g) mixture as the carrier gas is a promising way to enhance efficiency of the calcination process. Through the
LCPCLR, more alternative fuels can be used to reduce the operating cost, and CO2 emission is reduced by around 780 kg
per ton of lime manufacturing.

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Introduction

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An environment-friendly process for limestone calcination with CO2 ... https://www.sciencedirect.com/science/article/abs/pii/S0959652619330173

Due to the rapid industrialization, CO2 emission in China is significantly enhanced and occupies about 25% of the
world's total amount (National bureau of statistic, 2019, Peters et al., 2010, Shan et al., 2016). The industrial sector in
China as a major contributor which accounts more than 50% of the total national carbon emission (Liu et al., 2013, PR
China National Development and Reform Commision, 2004, Xu et al., 2017a, Xu et al., 2017b, Zhou et al., 2013).

Lime production is the second largest source of Chinese industry CO2 emissions (just behind the cement), but the
emission process has not been well studied. Lime is widely used in industry, e.g., using as a construction material, or
serving as an absorbent in flue gas desulfurization (Blasio et al., 2012, Xu et al., 2017a, Xu et al., 2017b, Jiang et al., 2019b)
and CO2 capture process (Diego et al., 2016, Yuan et al., 2018). According to the China Statistical Year Book published by
the National Bureau of Statistics (China), the annual yield of lime in China has exceeded 200 million tons, accounting for
around 70% of the global production (National bureau of statistic, 2019). Large lime production results in huge CO2
emissions. The greenhouse gas emitted from China's lime production increases from around 35 Mt CO2-eq to 140 Mt
CO2-eq from 1970 to 2009, occupying more than 60% of the world's emission in 2009 (European Commission, 2014).
However, most of the present researches focus on the CO2 emission from fossil fuel combustion (An et al., 2018, Ding
et al., 2017, Rahman et al., 2017) and cement production (Lin and Zhang, 2016, Xu et al., 2014, Zhang et al., 2018), while
few studies pay attention to the emissions from lime production (Gutiérrez et al., 2012). Xu et al. (2014) found that the
CO2 emission in China's cement industry can be reduced by 37%, 33%, 15%, and 15% by using clinker substitution, carbon
capture and storage, efficiency improvement and alternative fuel use, respectively. An et al. (2018) analyzed the
potential of CO2 reduction in China's iron and steel industry, which concluded that application of low carbon technology
is the most effective way to reduce carbon emission.

CO2 is mainly generated from fuel combustion in most industrial processes, whereas, in the lime production, the CO2
generation is dominated by the calcination stage. Limestone calcination constitutes
the main way to produce lime and has been widely applied. CO2 generated from the limestone calcination stage is called
as process emission. Through investigating CO2 emission from China's lime industry, Shan et al. (2016) found that the
process emission rapidly increased from 88.79 million tons (2001) to 141.72 million tons (2012). At present, the CO2
emitted from the CaCO3 decomposition is about 12 times and 31 times higher than that from fossil fuel combustion and
electricity consumption, respectively (Shan et al., 2016). The different generation mechanism makes it necessary to
develop different technologies to reduce the CO2 emission in the lime producing process (Benitez-Guerrero et al., 2018,
Fernández and Abanades, 2016, Li et al., 2017, Symonds et al., 2009, Wang et al., 2014).

The environmental performance of lime production can be enhanced by higher energy efficiency of the limekiln
(Gutiérrez et al., 2012). Parallel Flow Regenerative Kiln and Annular Shaft Limekiln are two efficient shaft kilns for
limestone calcination, whose thermal efficiency are 87% and 77%, respectively (Piringer, 2017, Senegačnik et al., 2008).
The energy consumption (kJ/kg lime) of the advanced shaft kilns are about 30% lower than rotary kiln (Senegačnik et al.,
2008, Shan et al., 2016). In addition to the development of advanced lime kilns, optimization of the operating process
can also enhance the heat efficiency (Deng et al., 2011, George et al., 2010). For example, Deng et al. (2011) developed a
lime shaft kiln diagnostic expert system, which can increase the decomposition rate of limestone by 6% and decrease
the coke ratio by 20%. The main aim of the above technologies is to improve the kiln heat efficiency where the CO2 from
fuel combustion can be reduced indirectly. However, the generated and emitted CO2 due to the CaCO3 decomposition
has not been addressed yet.

To fill this gap, an efficient and environment-friendly Limestone Calcination Process with CO2 Looping and Recovery
(LCPCLR) is proposed and investigated by thermodynamic analysis in this paper. A separate heater is included in the
LCPCLR system, and the CO2 (as heat carrier) transports heat from the heater to the calcination kiln. First, the thermal
balance analysis of LCPCLR system is carried out. Then, the effect of CO2 pressure and temperature on CaCO3
decomposition in pure CO2 environment is investigated based on the shrinking-core model. Third, the effect of gas-solid
water equivalent ratio on limestone calcination is discussed. Finally, a gas mixture of H2O(g) and CO2 is proposed to
replace pure CO2 as heat carrier to improve the calcination performance.

Section snippets

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An environment-friendly process for limestone calcination with CO2 ... https://www.sciencedirect.com/science/article/abs/pii/S0959652619330173

Limestone calcination process with looping CO2 as heat carrier

CaCO3(s) decomposition is the main chemical reaction in limestone calcination, where CO2 is generated along with the
product CaO. Unlike the traditional technology which emits the CO2 into the atmosphere directly, the LCPCLR system
proposed in this paper can recover the CO2 from the process. Fig. 1 shows the schematic diagram of the LCPCLR. The
LCPCLR consists of a shaft limekiln, separate heater, dust filter and CO2 storage equipment. The fossil fuel is burned in a
separate heater, and CO2…

Model of limestone calcination

The shrinking-core model is adopted to describe the calcination of limestone ore, as shown in Fig. 2. The limestone ore is
regarded as a solid sphere in the model. The generated CaO gathers on the outer surface, and the decomposition
reaction of CaCO3 occurs on the interface.

The radius r of CaCO3 decreases with the proceeding of the chemical reaction, and the decomposition ratio δ is related
to initial radii (r0) and instantaneous radii (r) of CaCO3, as described by Eq. (9).

In this…

Effect of temperature and pressure on limestone calcination

The CaCO3 decomposition is influenced by the ambient temperature and pressure (especially the PCO2). To understand
how the reaction can be affected in a pure CO2 environment, modeling analyses of CaCO3 decomposition based on the
shrinking-core model are conducted. In a pure CO2 environment, the decomposition time is usually used to represent
the calcination efficiency (Ar and Doğu, 2001). Here, in order to focus on the effect of temperature and CO2 pressure on
limestone calcination, a…

Performance improvement by introducing H2O(g) into LCPCLR

In the LCPCLR system, CO2 generated from CaCO3 decomposition stage is enriched and recycled. The heat capacity of the
heat carrier, PCO2 and temperature are the key factors for developing an efficient LCPCLR. In order to achieve a better and
more controllable system, a mixing gas containing CO2 and H2O(g) is proposed to replace the pure CO2 as the heat
carrier. The main advantages are as follow.
(1) The CO2 partial pressure can be easily regulated via using CO2/H2O(g) as the carrier gas. Due to the…

Conclusions

In this work, an efficient and environment-friendly Limestone Calcination Process with CO2 Looping and Recovery
(LCPCLR) is proposed. And the CaCO3 decomposition process in LCPCLR is investigated by thermodynamic analysis
under different temperatures (1000–1200 K) and CO2 pressures (0.001–1 atm).

The CaCO3 decomposition occurs in a pure CO2 environment in the now process. The mass flow rate of CO2 for recovery
occupies about 12–16% of that for looping in a typical LCPCLR system (100–150 t/d…

Acknowledgement
This work was supported by the National Key R&D Program of China (No. 2018YFB0605900).…

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Citation Excerpt :
…Improving the energy efficiency and using lower fossil-carbon-intensive fuels can reduce greenhouse gas emissions (Hills et al.,
2017). Carbon capture and storage (CCS) technologies have been investigated to reduce CO2 emissions in the lime industry (Jiang et al.,
2019; Chao et al., 2021; Edenhofer, 2015; International Energy Agency, 2013). Common technologies for carbon capture are listed in
Table 2.…

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