Fuel 167 (2016) 17–24

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Structurally improved CaO-based sorbent by organic acids for high

temperature CO2 capture
Yingchao Hu, Wenqiang Liu ⇑, Jian Sun, Mingkui Li, Xinwei Yang, Yang Zhang, Xiaowei Liu, Minghou Xu ⇑
State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074, China

h i g h l i g h t s

A comprehensive comparison of modified sorbents by 8 different acids was reported.

For the first time, 3 organic acids were used to modify the CaO sorbent.

Improved structure was achieved through the acidification-decomposition process.

Superior performance of the modified sorbent was proved under oxy–fuel calcination.

a r t i c l e i n f o a b s t r a c t

Article history: The acidification-decomposition process was used to enhance the performance of the natural limestone.
Received 5 July 2015 A series of potential organic acids was employed to modify limestone to produce CaO-based sorbents for
Received in revised form 7 October 2015 high temperature CO2 capture. The organic acids studied include formic acid, acetic acid, propionic acid,
Accepted 13 November 2015
citric acid monohydrate, oxalic acid dihydrate, lactic acid, L-()-malic acid, and L-(+)-tartaric acid.
Available online 21 November 2015
Particularly, the latter three are novel acids used for the first time to modify limestone to obtain the
CaO-based sorbents. The cyclic carbonation–calcination performance of the sorbents was investigated.
Keywords:
All the sorbents, except the one modified by formic acid, exhibit the improved performance for capturing
CO2 capture
CaO-based sorbent
CO2. In particular, the novel sorbent modified by L-(+)-tartaric acid (S–T) shows the best cyclic perfor-
Organic acid mance with a high carbonation conversion of 36% at the 26th cycle, almost twice of that of unmodified
Modification sorbent. The superior performance of this sorbent was also found when tested under the simulated oxy–
fuel atmosphere (realistic calcination atmosphere for post-combustion CO2 capture). It is believed that
the improved structure by organic acid, which is in favor of mitigating the sintering and loss of specific
surface area (SSA), has contributed to the superior performance of the sorbent.
Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction gases) and then achieving a high concentration of CO2 for the sub-
sequent utilization and storage. In addition, CLP has also been rec-
The technology of carbon capture, utilization and sequestration ognized as the basis of a few new technologies rather than post-
(CCUS) has been widely accepted as one of the effective approaches combustion capture, aiming to control the emission of CO2, such
to help mitigate global warming [1], which is caused by the emis- as the Japanese hydrogen production by reaction integrated novel
sion of greenhouse gases, in particular CO2. Calcium Looping Pro- gasification (HyPr-RING) process [4] and the American zero emis-
cess (CLP), as one of the CO2 capture technologies proposed up to sion coal alliance (ZECA) process [5–7].
now, has attracted extensive attention worldwide [2,3]. In the However, the cyclic CO2 capture capacity of CaO-based sor-
post-combustion system, this process is based on the circulation bents, especially the sorbents from naturally occurring limestone
of CaO-based sorbents between the carbonation reactor and regen- and dolomite, generally sharply decreases after only several cycles
eration reactor, hence separating CO2 from gas mixture (i.e., flue [8–14]. The sintering of CaO/CaCO3, particularly CaCO3, is believed
to be the main cause for the loss-in-capacity of CaO-based sor-
bents, owing to the much higher carbonation temperature
⇑ Corresponding authors at: State Key Laboratory of Coal Combustion, Huazhong
(650 °C) and calcination temperature (900 °C) than Tammann
University of Science & Technology, 1037 Luoyu Road, Wuhan 430074, China. Tel.:
+86 27 87542417x8301; fax: +86 27 87545526.
temperature (533 °C) of CaCO3 [15,16]. As a result of severe sin-
E-mail addresses: [email protected] (W. Liu), [email protected] tering, the physical aggregation of the sorbent grains occurs, which
(M. Xu). in turn leads to the reduction of the pore volume and surface area

http://dx.doi.org/10.1016/j.fuel.2015.11.048
0016-2361/Ó 2015 Elsevier Ltd. All rights reserved.
18 Y. Hu et al. / Fuel 167 (2016) 17–24

of CaO-based sorbents [17–21]. To allow the new technology even- (see Fig. 1). The sample pan, loaded with 1 g sample, can be
tually becoming reality, researchers have spared no efforts to shifted between the calciner and the carbonator and the weight
investigate various methods on solving this problem. These meth- variation was measured by a high precision electronic balance.
ods used in the literature include: (i) modifying naturally occurring The calcination process was performed at 900 °C under a N2 or
minerals by organic acids [22–28]; (ii) hydration treatment to CaO oxy–fuel (O2:CO2 = 27:73) atmosphere for 10 min. The carbonation
to reactivate the sorbents [12,29–35]; (iii) acquiring CaO from new process was with 15% CO2 (balanced with N2) at 600–700 °C for
calcium precursors [18,36–39]; (iv) incorporating CaO into 30 min. The total flow rate of the gases for both calcination and
sintering-resistant inert supports [40–45]. carbonation processes was controlled at 2 L/min. When oxy–fuel
Among these methods, the acidification of natural limestone or calcination atmosphere was used, O2/CO2 gas mixture was quickly
dolomite exhibits a promising prospect to improve the perfor- purged off by N2 before the sorbents was shifted to the carbonator,
mance of CaO-based sorbents. As early as in 2008, Li et al. [22] in order to prevent the sorbents from reacting with the CO2 that
found that the dolomite modified with acetic acid solution existed in oxy–fuel atmosphere. All the sorbents studied in this
achieved a high carbonation conversion of 60% at the 20th carbon- work were tested over 26 cycles.
ation/calcination cycle, 2.3 times as high as that of the original one The performance of the modified sorbents and unmodified one
under the same experimental conditions. Later, their group has was evaluated by the maximum carbonation conversion, defined
reported the positive effectiveness of a series of acids, including as follows:
acetic acid, pyroligneous acid (mainly consisting of acetic acid, for-
m  m1 W CaO
mic acid and propionic acid) and propionic acid, on the modifica- Xn ¼  100% ð1Þ
tion of limestone [23–25,28]. Other organic acids such as citric m1  m0 W CO2
acid [26], formic acid [27] and oxalic acid [27] have also been where Xn represents the maximum carbonation conversion at nth
proved to be able to improve the performance of limestone. cycle, m is the mass of the sorbent together with the sample pan
However, there is not yet a comprehensive investigation on the after carbonation at each cycle, m1 is the initial mass of sample
comparisons of the modified natural limestone by the abovemen- pan loaded with the sorbent, m0 is the mass of the sample pan,
tioned organic acids, when testing under the same experimental WCaO and WCO2 are the mole mass of CaO and CO2, respectively.
condition. Meanwhile, it is also unclear whether there are any
other potentially more effective organic acids for the modification.
2.3. Characterization
Hence in this work, we intend to compare the performance of mod-
ified limestone by 8 different organic acids (including 3 new
The microstructure characteristics of the sorbents were ana-
organic acids) under the same test conditions, attempting to iden-
lyzed via field emission scanning electron microscopy (FSEM; Nova
tify the best organic acid to modify natural CO2 sorbents. The
NanoSEM 450, FEI Inc). The specific surface area and pore volume
microstructure characteristics and the specific surface area of the
were determined by accelerated surface area and porosimetry sys-
sorbents were examined to evaluate the effectiveness of the mod-
tem (ASAP2020, Micromeritics) using nitrogen adsorption–desorp-
ification and the performances of the sorbents during multicyclic
tion isotherms at 77 K. The specific surface area was estimated
carbonation–calcination tests were assessed.
using Brunauer–Emmett–Teller (BET) equation. The diffraction
2. Experimental patterns of the sorbents’ phase composition were examined by
X-ray diffraction (XRD, Empyrean, PANalytical B.V.) with 2h rang-
2.1. Preparation of sorbents ing from 10° to 90° using Cu Ka radiation (k ¼ 0:15406 nm).

CaO-based sorbents tested in the present work were produced 3. Results and discussion
from naturally occurring limestone (containing 98.5 wt% CaCO3,
particle size < 150 lm) modified with 8 different organic acids, 3.1. Analysis on the acidification and thermal decomposition processes
including formic acid (98%, Sinopharm), acetic acid (99.5%, Sino-
pharm), propionic acid (99.5, Sinopharm), citric acid monohydrate It is believed that the acidification and thermal decomposition
(99.5%, Sinopharm), oxalic acid dihydrate (99.5%, Sinopharm), lac- processes during the sorbents preparations are the major contribu-
tic acid (85.0%, Sinopharm), L-()-malic acid (98.5%, Sinopharm), tions to the structural differences, and thus the performance differ-
and L-(+)-tartaric acid (99.5%, Sinopharm). Among these acids, lac- ences of produced sorbents. Therefore, it is valuable to investigate
tic acid, L-()-malic acid and L-(+)-tartaric acid were used for the these two processes.
first time to modify natural CO2 sorbents. In the modification pro- The acidification processes of the limestone (CaCO3) proceed on
cess, a certain amount of limestone was treated with excess the basis of the chemical reaction equations listed in Table 1. The
organic acids in a beaker, accompanied with four-hour stirring subsequent decompositions of organic calcium compounds, which
and heating process in an electric-heated thermostatic water bath was previously formed in the course of acidification, was analyzed
to ensure the full acidification of the limestone. The mixture in the in a thermogravimetric analyzer (TGA, Perkin Elmer Pyris 1). About
beaker was subsequently subjected to overnight drying at 105 °C in 80 mg sample was placed in the pan and then was heated to 900 °C
a drying oven and then the powder obtained after previous drying under a rate of 5 °C/min. The temperature was held for 10 min at
process was calcined for 2 h at 900 °C in a muffle furnace under N2 900 °C, before being cooled down at the rate of 20 °C/min to room
atmosphere. The nomenclature for the modified sorbents is as fol- temperature. The whole processes were conducted under nitrogen
lows: S–X, where X is the first letter of the corresponding organic atmosphere.
acids, as summarized in Table 1. The unmodified sorbent (named It is known that only one weight loss peak occurs for the natural
as S–UL), directly produced from the limestone, was also investi- limestone (decomposing CaCO3 to CaO). In comparison, the ther-
gated for comparison purposes. mograms (Fig. 2) indicate three or four obvious weight loss peaks
during the decompositions of the acidified calcium compounds. It
2.2. Performance test of sorbents is also worth noting that the acidified calcium compounds consist
of organic calcium and dried organic acids powders, because the
The cyclic carbonation–calcination performance experiment of excess acids were used during the acidification process. These
the sorbents was conducted in a dual fixed bed quartz reactor weight losses include following stages: (i) dehydration (only for
 Y. Hu et al. / Fuel 167 (2016) 17–24 19

Table 1
Chemical reactions of the acidification with different organic acids.

Organic acids Reactions of acidification Nomenclature of final sorbents

Formic acid CaCO3ðsÞ þ 2CH2 O2ðaqÞ ! CaðHCO2 Þ2ðaqÞ þ CO2ðgÞ þ H2 OðlÞ S–F
Acetic acid CaCO3ðsÞ þ 2CH3 CO2 HðaqÞ ! CaðCH3 CO2 Þ2ðaqÞ þ CO2ðgÞ þ H2 OðlÞ S–A
Propionic acid CaCO3ðsÞ þ 2C3 H6 O2ðaqÞ ! CaðC3 H5 O2 Þ2ðaqÞ þ CO2ðgÞ þ H2 OðlÞ S–P
Citric acid monohydrate 3CaCO3ðsÞ þ 2C6 H8 O7  H2 OðsÞ ! Ca3 ðC6 H5 O7 Þ2ðsÞ þ 3CO2ðgÞ þ 5H2 OðlÞ S–C
Oxalic acid dihydrate CaCO3ðsÞ þ C2 H2 O4  2H2 OðaqÞ ! CaC2 O4ðsÞ þ CO2ðgÞ þ 3H2 OðlÞ S–O
Lactic acid CaCO3ðsÞ þ 2C3 H6 O3ðaqÞ ! CaðC3 H5 O3 Þ2ðaqÞ þ CO2ðgÞ þ H2 OðlÞ S–L
L-()-malic acid CaCO3ðsÞ þ C4 H6 O5ðaqÞ ! CaC4 H4 O5ðsÞ þ CO2ðgÞ þ H2 OðlÞ S–M
L-(+)-tartaric acid CaCO3ðsÞ þ C4 H6 O6ðaqÞ ! CaC4 H4 O6ðaqÞ þ CO2ðgÞ þ H2 OðlÞ S–T

Fig. 1. Schematic illustration of the dual fixed bed quartz reactor.

under the same conditions, in order to verify the effectiveness of

different acidifications. In this experiment, the modified sorbents
by reported organic acids [22–28,46–48] and three novel acids
were all tested and compared under a ‘conventional’ condition of
carbonation at 650 °C under 15% CO2, and calcination at 900 °C
under 100% N2.
The comparisons of the performance of these sorbents over 26
cycles are given in Fig. 3. The 26-cycle run were conducted by a
14-cycle run followed by a 12-cycle one of next day. The sorbents
was hydrated by the air moisture during the time interval of over-
night between two runs. The hydration has led to a small increase
of conversion during the first cycle of the 2nd run. However, the
conversion quickly fell back and continued its original decreasing
trend during subsequent cycles.
In comparison with the unmodified calcium oxide sorbent, all
sorbents modified with organic acids except formic acid exhibit
Fig. 2. The thermograms of the organic calcium and original limestone.
an enhanced performance at the last cycle (i.e., the improved
the hydrous organic calcium); (ii) decomposition of the excess last-cycle conversion). This exception disagrees with results by
organic acid; (iii) decomposition of the organic calcium to calcium Ridha et al. [48]. The reason for this disagreement could be due
carbonate; and (iv) decomposition of calcium carbonate to calcium to the different limestone sources, acid solution concentrations
oxide.
It is believed that the acidification process and subsequent
decomposition process play a significant role in enhancing the per-
formance of the sorbents. The acidification process, acidifying cal-
cium carbonate to organic calcium, eventually increases its
molecular weight. Then the decomposition process, decomposing
organic calcium to calcium oxide, results in the sharp weight loss.
The porous structure of final product of CaO was obtained owing to
the pore-spaces formed by the weight loss during this process,
which greatly facilitates CO2 to diffusion into the inner of CaO
grains to be captured. Therefore, the pore-spaces improvement
induced by the acidification-decomposition process effectively
enhances the performance of the modified sorbents.

3.2. Comparison of the performance of various modified sorbents

under cyclic carbonation/N2 calcination tests

The performance of the sorbents will be varied at different Fig. 3. Performance of the sorbents under conventional N2 condition (calcination:
experimental conditions, and hence it is necessary to test them 900 °C, N2, 10 min; carbonation: 650 °C, 15% CO2, 30 min).
20 Y. Hu et al. / Fuel 167 (2016) 17–24

and treatment conditions (such as acidifying time, temperature a richer porosity in mesopores within 2–30 nm than the unmodi-
et al.) during acidification processes, which however needs a com- fied one (S–UL), which is probably responsible for the superior per-
prehensive study. It is interesting to note that the modification formance of S–T than that of S–UL. In addition, the better
with L-(+)-tartaric acid, which was not reported in the literature, performance of S–T than S–UL at the 26th carbonation/N2 calcina-
is more effective than others. The last-cycle conversions of all the tion cycle is probably attributed to the more abundant pores with
sorbents can be ranked as follows: S–T > S–P > S–M > S–A > S– size in the 50–100 nm region, the pores within which contribute a
C > S–L > S–O > S–UL > S–F. lot to the capture of CO2 [52–54].
Fig. 4 compares the conversion performance of our modified
sorbents and that in the literature. The selection criteria of the con-
version is strictly on the basis of the following orders: (1) at the 3.3. Sorbent performance during cyclic carbonation/oxy–fuel
longest cycle; (2) under the most severe experimental conditions; calcination tests
(3) with the highest conversion. It is found that most last-cycle
conversions of the modified sorbents with organic acids are The regeneration process of CLP, which is based on the reversi-
between 30% and 35%. The last-cycle conversion of S–T tested with ble reaction of CaCO3 $ CaO þ CO2 ; DH ¼ þ178 kJ=mol, is an
oxy–fuel calcination is also presented here (detailedly discussed in exothermic reaction requiring additional energy to decompose
the later section). Besides organic acids, inorganic acids could also CaCO3. When CLP is used for post-combustion CO2 removal of flue
be employed to modify sorbents (the results are not presented in gas for coal-fired power plants, which was originally proposed as
Fig. 4). For example, the sorbent doped with HBr obtained an early as in 1999 by Shimizu et al. [55], the energy is from the
improved residual conversion of 13%, compared to only 5% of oxy–fuel combustion of coal. Thus, the concentrated CO2 in the
the undoped one [49]. It is worth noting from the figure that outlet of regenerator would be achieved, both from CaCO3 decom-
L-(+)-tartaricacid is still the most effective ones when tested under position and coal combustion with pure oxygen, facilitating the
the same test conditions in our study. subsequent compression and sequestration. Hence it is of signifi-
It is proposed that the morphology changes (e.g., specific BET cant importance to investigate the performance of the modified
surface area, SSA and pore size distribution), in the course of acid- sorbents under oxy–fuel calcination condition.
ification and the subsequent decomposition from organometal to One of the typical gas atmosphere of oxy–fuel combustion is
oxide, can effectively enhance CO2 capture performance. Fig. 5 pre- 27% O2 and 73% CO2 (O2:CO2 = 27:73) [56], and this gas atmo-
sents the schematic illustration of the modification process of the sphere at 900 °C for 10 min is used here during each calcination
most effective organic acid (e.g., S–T). It is found that both routes condition of the cyclic carbonation–calcination experiments. Two
produce the same the final product of CaO as reflected by the samples of S–T and unmodified sorbent were chosen to be tested.
XRD patterns. However, in comparison to the direct decomposition It is illustrated in Fig. 6 that the cyclic CO2 capture performance of
of limestone to CaO, the one with the modification process to pro- both samples becomes worse when the calcination condition is
duce CaO has the step of releasing 2C&2H2O&CO during the changed from conventionally used 100% N2 atmosphere to the
decomposition of CaC4H4O6 to CaCO3. The extra step could bring oxy–fuel atmosphere. However, it is expected that the S–T sorbent
more pores and reactive surface of the final product, allowing more still exhibits an advantage of CO2 capture over the unmodified one,
CO2 to react with the CaO, thus resulting in better capacity in cap- holding a relatively high conversion of 18.5% at the 26th cycle,
turing CO2. SSA of the modified sorbent (S–T) is 13.23 m2/g, almost twice as high as that (10.5%) of unmodified sorbent.
nearly a-quarter increase in comparison with that of the unmodi- The different degrees of sintering caused by two calcination
fied one (S–UL). This finding is consistent with the previous study conditions could explain the phenomena abovementioned, which
that the formation of microporous/mesoporous structures during can be reflected in the variation of the specific BET surface area
the decomposition processes of organometallic precursors could (SSA), pore size distribution and surface micromorphology. Table 2
effectively increase the SSA of sorbents [18,43,50,51]. It is also shows that the SSA of the sorbents after being calcined in oxy–fuel
found (see Fig. 7) that the sorbent after modification (S–T) acquires condition is 50% lower than that in N2 condition processes.
Besides, the pore size distribution of S–T depicted in Fig. 7 also
demonstrates the severer sintering under oxy–fuel calcination.
Both S–T and S–UL exhibit less abundant mesopores and macrop-
ores and narrower pore size distribution when the calcination
atmosphere changes from N2 to oxy–fuel condition. The reduced
SSA and deteriorated pore volumes are ascribed to the high CO2
concentration of oxy–fuel condition. It is generally believed that
the presence of CO2 during calcination process increases the com-
plete decomposition time of CaCO3 [57]. The prolonged decompo-
sition time results in a much longer exposure time of CaCO3 under
the high calcination temperature, causing severer sintering due to
the much lower sintering temperature (Tammann temperature) of
CaCO3 (533 °C) than that of CaO (1313 °C) [43]. The findings are
consistent with those reported in the literature. [57–60], where it
has been found that the sintering of the sorbent can be accelerated
by the presence of CO2. It is worth noting that S–T owns higher SSA
than unmodified sorbent no matter which calcination atmosphere
was used, indicating the positive effect of the L-(+)-tartaric acid
modification process on the sintering-resistant property of the
sorbents.
The surface micromorphology changes (depicted in Fig. 8) of the
sorbents are in accordance with the variation of SSA. It is revealed
from the FSEM images that the sorbents (both S–T and S–UL) expe-
Fig. 4. Last-cycle conversion of our modified sorbents and that in the literature. rienced a more severe sintering and aggregation of grains when
 Y. Hu et al. / Fuel 167 (2016) 17–24 21

Fig. 5. Schematic illustration of the modification process.

Fig. 6. Cyclic carbonation conversion of the sorbents under N2 calcination condi-

tion, and oxy–fuel calcination condition (calcination: 900 °C, 100% N2 or O2: Fig. 7. Pore size distribution for S–T and S–UL.
CO2 = 27:73, 10 min; carbonation: 650 °C, 15% CO2, 30 min).

Table 2 carbonation temperatures. Hence it is also interesting to find out

Specific surface area (SSA) of the sorbents before and after cycles. the optimum carbonation temperatures for our sorbents, particu-
Sorbents Before cycles After cycles (N2) After cycles (oxy–fuel) larly the one modified by L-(+)-tartaric acid (S–T) that was found
(m2/g) (m2/g) (m2/g) to have the best CO2 capture performance.
S–UL 10.75 3.34 1.80 It has been reported that CaO-based sorbents have the highest
S–T 13.23 4.68 2.31 conversion when carbonated at the temperature range of 600–
700 °C [61]. Therefore, three carbonation temperatures of 600,
650 and 700 °C were tested in the current study. Fig. 9 compared
calcined in oxy–fuel condition compared to that in N2 calcination the cyclic conversions of the sorbent S–T over 26 cycles, when car-
condition. However, the modified sorbent of S–T always exhibits bonated at the selected three different temperatures (calcined
a micromorphology with more pores and less degree of aggrega- under the same oxy–fuel condition at 900 °C). It is interesting to
tion of grains than the unmodified one, which is another evidence find that S–T exhibits a quite low CO2-capture activity under the
of the modification on the resist of the sintering of the sorbent. carbonation temperature of 600 °C, which is consistent with the
results of the previous study [23,24,26]. However, when the car-
3.4. Effect of carbonation temperature on the performance of S–T bonation temperature is elevated, much higher conversions are
observed. The conversion at the 1st carbonation are as high as
Previous studies by Li et al. [23,24] have indicated that the sor- 81% at both carbonation temperatures of 650 and 700 °C, which
bents modified with different organic acids own different optimum decay to 18% and 24% at the 26th carbonation, respectively. It
22 Y. Hu et al. / Fuel 167 (2016) 17–24

Fig. 8. Surface micromorphology of the sorbents before and after 26 cycles under different calcination atmospheres: A: S–UL, before cycles; B: S–UL, after cycles, N2; C: S–UL,
after cycles, oxy–fuel; D: S–T, before cycles; E: S–T, after cycles, N2; F: S–T, after cycles, oxy–fuel.

temperatures probably lie in the activation of the CO2 diffusion

process with higher carbonation temperature to get through the
CaCO3 product layer previously formed in the chemical reaction
controlled stage [62]. Thus the increased rate of diffusion retards
the transition from the chemical reaction controlled stage to the
diffusion controlled stage [63] and therefore the conversion is
improved.

4. Conclusions

The modification of natural occurring limestone with organic

acids is able to effectively improve the performance of CaO-based
sorbents. This work aims to make a comprehensive comparison
of sorbents modified with a range of organic acids, including three
acids that have not been reported. This study indicated that all
organic acids except formic acid show the capacity of enhancing
Fig. 9. Performance of S–T under different carbonation temperatures (calcination: the sorbents’ performance. It has been reported for the first time
900 °C, O2:CO2 = 27:73, 10 min; carbonation: 650 °C, 15% CO2, 30 min). that the sorbent modified with the L-(+)-tartaric acid (S–T) exhib-
ited the highest carbonation conversion at the 26th cycle. More-
can be concluded from the finding that 700 °C is the optimum over, it holds a conversion of nearly twice as high as that of the
carbonation temperature for the sorbent S–T. The reasons for unmodified one at the 26th cycle, during the carbonation/oxy–fuel
the different sorbent performance under varied carbonation calcination cyclic tests. The corresponding specific surface area
 Y. Hu et al. / Fuel 167 (2016) 17–24 23

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