Fuel 86 (2007) 1396–1401

[Link]fi[Link]

Effect of coal soluble constituents on caking property of coal

Hengfu Shui *, Mingdong Zheng, Zhicai Wang, Xunming Li
School of Chemistry and Chemical Engineering, Key Laboratory of Anhui Educational Department, Anhui University of Technology,
Maanshan 243002, Anhui Province, China

Received 14 August 2006; received in revised form 16 November 2006; accepted 17 November 2006
Available online 18 December 2006

Abstract

Three cokemaking bituminous coals were extracted by the CS2/NMP mixed solvents with different content of NMP, and the effect of
the amount and the component of coal soluble constituents on the caking property of the extracted residues of coals were investigated in
this study. The CS2/NMP mixed solvent (1:1 by volume) was found to give the maximal extraction yields for the three coals, and the fat
coal gave the highest extraction yield of 78.6% (daf) corresponding to its highest caking index of 101. It was found that for coking coal,
when the extraction yield got to the maximum of 25.3% in the 1:1 by volume of CS2/NMP mixed solvent, the residue extracted still had
caking property with the caking index of 19. This means parts of the caking constituents of coal are un-extractible because of covalent
bonding or strong associative cross-links. The soluble components extracted by the CS2/NMP mixed solvent and their effects on the
caking indexes of the residues at a similar extraction yield quite differed depending on the NMP content in the mixed solvent. The coal
solubles extracted by the CS2/NMP mixed solvent with NMP less than 50% contained less light constituents with less of oxygen groups.
This may lead to the decrease in the caking indexes for the residues obtained at the similar extraction yields compared to those of the
CS2/NMP mixed solvent with NMP more than 50%.
Ó 2006 Elsevier Ltd. All rights reserved.

Keywords: Coal; Caking property; Soluble constituent

1. Introduction ization is one of the important utilizations of coal and the

caking property of coal is a key factor to control the qual-
With the development of iron and steel industry and the ity of coke. When coal is heated to 370–400 °C, it begins to
increased size and throughput of blast furnace, the role of soften and form a coherent porous plastic mass, which can
coke as a permeable support becomes greater in impor- swell to fill a container larger than its original volume. On
tance due to the pulverized coal injection. In such condi- further heating and subsequent cooling, the mass contracts
tions, a decrease in coke rate produces a decrease in the and some cracking occurs but quite large strong lumps of
thickness of coke layer in the stack and cohesive zone coke can remain [2]. The quantity and quality of the plastic
together with an increased residence time of coke in the mass dominate the quality of coke formed. The quantity
lower part of the blast furnace. Coke residence times and quality of plastic mass formed depend on the release
increase by 30% with variations in coal rate from 200 to of low melting donor hydrogen rich species already present
100 kg coal/t hot metal. This means that coke is subject within the coal structure. They serve as mobile hydrogen
to longer periods under mechanical, thermal, and chemical donors able to stabilize radical fragments being split from
stresses that further increase coke degradation in the blast the coal macrostructure and to convert them into ‘solvat-
furnace [1]. All of these provide a special quality require- ing’ species, i.e. those radical fragments stabilized by
ment for coke to adapt modern blast furnace. Coal carbon- hydrogen donor. With the temperature increasing, the pro-
duction of radical fragments increases, and the level of flu-
*
Corresponding author. idity of the plastic mass development eventually reached
E-mail address: shhf@[Link] (H. Shui). depends on how efficiently these are able to contact donor

0016-2361/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/[Link].2006.11.027
 H. Shui et al. / Fuel 86 (2007) 1396–1401 1397

hydrogen anywhere within the coal to generate additional Coal (1.5 g) and CS2/NMP mixed solvent were charged
‘solvating’ species [3]. into centrifuge tube to be extracted for 30 min under ultra-
Understanding the caking mechanism during coal car- sonic (38 Hz) irradiation at room temperature. The mixture
bonization is very important for opening the coal of coke- was filtered by filter membrane (0.8 lm) after centrifuga-
making resources and increasing the quality of coke. The tion for 50 min at 14000 rpm. The residue was exhaustively
early researchers [4] found that the content of solvent sol- extracted with fresh mixed solvent about 6 times in the
ubles of coal has a great effect on the caking property of same way until the filtrate became almost colorless. The
coal. For example, when coal was extracted with chloro- residue was washed with acetone three times, and dried
form and pyridine, it can be fractionated into a-, b- and in vacuum at 353 K overnight. The extraction yield was
c-fractions, and the c-fraction, which is chloroform solu- determined from the weight of the residue:
ble, is the key constituent for coal caking property. It has
1  M r =M coal
long been realized that chloroform solubles obtained from Extraction yield ¼  100%
coal itself play an important role in modifying the property ð100  Ad Þ=100
of the plastic mass. There is a reasonable correlation where Mr is the weight of the residue (g), Mcoal is the
between fluidity level of the plastic mass of coal and the
weight of coal (g), and Ad is the ash content of coal (db,%).
amount of chloroform solubles that coals regain their abil-
ity to soften when chloroform solubles are returned to the
insoluble residue, and that adding chloroform solubles to 2.3. Caking index measurement
coals lower their softening temperature.
The solubles of coal really affect its caking propensity, The caking index (G) was used to characterize the caking
and the effect of coal soluble constituents on its caking pro- property of coal. Its measurement was carried out accord-
pensity depends on the solvent used to obtain the coal sol- ing to GB5447-85 (national standard of China). The mea-
uble constituent. For example, chloroform solubles of coal surement method of G index is based on Roga index,
have a greater effect on the caking property of coal com- which is known worldwide. One gram of coal was mixed
pared to pyridine solubles. Iino et al. [5,6] found that the with 5 g of standard anthracite, and the mixture was car-
carbon disulfide-N-methyl-2-pyrrolidinone (CS2/NMP) bonized at 850 °C for 15 min. (The coke obtained was car-
mixed solvent (1:1 by volume) is a uniquely powerful sol- ried out drum test two times, which is different from Roga
vent for the extraction of some bituminous coals. It gives index of three times drum tests). The coal sample prepara-
74% of extraction yield for one kind of Chinese fat coal tion, stirring, carbonization and drum test are the same as
[7]. In this study, we will discuss about the effects of coal those of Roga index measurement, and the caking index G
soluble constituents on its caking propensity by use of was calculated as:
the CS2/NMP mixed solvents with different content of 30m1 þ 70m2
NMP, and some interesting results were obtained. G ¼ 10 þ
m

2. Experimental where m is the weight of coal sample (g), m1 is the weight of

coke (g) > 1 mm fractions after coke abrasion (the first
2.1. Coal sample drum test), and m2 is the weight of coke (g) > 1 mm frac-
tions after the second drum test.
Three coals of cokemaking with different ranks were
obtained from Maanshan Iron & Steel Co. LTD. (China), 2.4. TG and FTIR measurements
and the properties of coals are listed in Table 1. Coal sam-
ple was dried in vacuum at 353 K overnight before use. Thermo gravimetric (TG) analysis was carried out on a
SHIMADZU TG60 analyzer. About 10 mg of sample was
2.2. Coal extraction placed in an alumina pan and heated from 25 °C to 800 °C
at a rate of 10 °C/min under 50 ml/min nitrogen gas flow.
Coal extraction with CS2/NMP mixed solvent was car- FTIR were measured by a PE-Spectrum One IR spectrom-
ried out at room temperature, as described elsewhere [5]. eter at a resolution of 4 cm[Link] samples for FTIR

Table 1
Ultimate and proximate analyses of coals
Coal Ultimate analysis (%, daf) Proximate analysis (%) G
C H N S Oa Moisture (air dried) Ash (dry) VM (daf)
Gas coal 81.0 4.8 1.2 0.6 12.5 8.5 8.0 37.7 87
Fat coal 86.6 4.2 0.8 1.9 6.5 5.8 8.38 33.9 101
Coking coal 87.9 5.1 1.0 0.2 5.9 4.2 8.98 20.2 90
a
By difference.
1398 H. Shui et al. / Fuel 86 (2007) 1396–1401

measurement were prepared by mixing coal sample with 80

KBr and the mixture was pressed into a pellet.
fat coal

Extraction yield, wt%(daf)

3. Results and discussion
60
3.1. Extraction yields of coals in CS2/NMP mixed solvent
with different mixed ratios of NMP
gas coal
40
Three coals with different ranks, i.e. gas coal, fat coal
and coking coal, were extracted in CS2/NMP mixed solvent
with different mixed ratios of NMP (in volume), at room
temperature as shown in Table 2 and Fig. 1 was also 20
obtained based on the data given in Table 2. coking coal
Among the three coals, fat coal gives much higher
extraction yield in the same NMP content in the mixed sol- 0
vent compared to those of the other coals, which is coinci- 0 10 20 30 40 50 60 70 80 90 100
dent with its higher caking index of 101. However, gas coal NMP mixed ratio, %
gives higher extraction yield than coking coal, but its cak-
Fig. 1. Extraction yields of coals in the CS2/NMP mixed solvents with
ing index (87) is a little lower than that of coking coal (90). different NMP mixed ratios.
This may demonstrate that not only the amount of solubles
in the coal but also the solubles components affect the cak-
ing property of coal. It is interesting to note that the max- The difference of extraction yields between CS2/NMP
imum extraction yields for the three coals were all obtained mixed solvent with 1:1 by volume and NMP was defined
in the CS2/NMP mixed solvent with 1:1 by volume. Iino as given below:
et al. [5] found that the CS2/NMP mixed solvent with 1:1 YM  YN
by volume gave maximal extraction yields for some bitumi- Difference ð%Þ ¼  100
YM
nous coals. Shui et al. [8] found that for the CS2/NMP
mixed solvent with 1:1 volume ratio, it gave the strongest where YM is the extraction yield of coal with CS2/NMP
absorbance in the peak of 1508 cm1 in FTIR spectrum, mixed solvent (1:1 by volume) and YN is the extraction
suggesting that there is a strong interaction between CS2 yield of coal with NMP. The differences of the extraction
and NMP in the mixed solvent of 1:1 volume ratio and this yields calculated for gas coal, coking coal and fat coal
interaction may disrupt the dipole based association of are 40.9%, 61.7% and 71.9% respectively. One can easily
NMP thus making lower viscosity of the mixed solvent, understand that for gas coal, its network structure is looser
penetrating more quickly into the structure and swelling among the three coals because of its lower aromaticity,
the coal macromolecular structure, resulting in the larger much of substituted side chains due to its lower coalifica-
solvent partner (NMP) to enter and break the stronger tion. This will let high viscosity of NMP enter the most
coal–coal interactions. of network of the gas coal resulting in the extraction yield

Table 2
Extraction yields of coals in the CS2/NMP mixed solvent with different content of NMP and the caking index of the residues obtained
Solvent ratio in the CS2/NMP mixed Gas coal Fat coal Coking coal
solvent
NMP content CS2 content (%) Extraction yield G Extraction yield G Extraction yield G
(%) (wt%, daf) (wt%, daf) (wt%, daf)
0 100 4.3 66 2.1 94 1.6 85
5 95 12.2 15 – – – –
10 90 16.6 0 34.0 82 2.6 83
20 80 21.0 – 51.3 49 6.3 70
25 75 – – 58.8 13 – –
30 70 27.4 – 67.1 0 12.1 61
40 60 28.9 – 71.4 – 17.2 30
50 50 34.2 – 78.6 – 25.3 19
60 40 31.5 – 76.3 – 21.6 27
70 30 30.5 – 75.8 – 18.8 41
80 20 29.6 – 70.5 0 15.6 54
85 15 – – 63.5 19 – –
90 10 28.1 – 52.4 61 12.9 63
100 0 20.2 – 22.1 89 9.7 67
 H. Shui et al. / Fuel 86 (2007) 1396–1401 1399

difference between the CS2/NMP mixed solvent (1:1 by vol- contents at the same extraction yields. For example, for
ume) and NMP decrease. However, large difference of fat coal when NMP content is 20% in the CS2/NMP mixed
extraction yields between the CS2/NMP mixed solvent solvent, the extraction yield is 51.3%, and the caking index
(1:1 by volume) and NMP for fat coal may show a higher of the residue is 49. However, when the NMP content
compacted network structure of fat coal because of non- increases to 90%, it gives an extraction yield of 52.4%
covalent bonds cross-links compared to that of coking (more than 51.3%), but the caking index of the residue is
coal. One can deduce that the CS2/NMP mixed solvents 61, much larger than 49. Similar result can be observed
with different contents of NMP can enter the different net- for coking coal as shown in Fig. 2. The caking index of res-
work structures of coal, and give different soluble constitu- idue extracted with higher extraction yield should be lower
ents although their extraction yield may be similar. This for the same coal. However, our result shows that the res-
may be helpful for us to understand the effect of soluble idues obtained from the extraction of the CS2/NMP mixed
constituents on the caking property of coal. solvents in NMP less than 50% give lower caking indexes
for the same coal compared to the residues from the
3.2. Effect of extraction of coal on the caking index of the NMP more than 50% of the CS2/NMP mixed solvents
residue although they have similar extraction yields or even a little
lower extraction yields for using the NMP less than 50% of
Fig. 1 shows that with NMP content changing in the the CS2/NMP mixed solvents. The results strongly demon-
CS2/NMP mixed solvent, the extraction yields for the three strate that the soluble constituents from the CS2/NMP
coals are different. In order to probe the relation between mixed solvents in NMP less than 50% and more than
the amount of solubles and the caking property of coal, 50% are different although they may have similar extrac-
we measured the caking indexes of the residues extracted tion yields. Because of the difference in soluble constitu-
with different extraction yields by different NMP mixed ents, the caking indexes of residues obtained are different.
ratios in the CS2/NMP mixed solvent as shown in Fig. 2. In order to further understand the property of the resi-
Clearly, Fig. 2 shows that with the extraction yields dues with similar extraction yields obtained from the
increasing, the caking indexes of residues from the three CS2/NMP mixed solvent with different NMP content, TG
coals decrease. For fat coal, when the extraction yield and FTIR analyses were carried out for the coal extraction
reaches about 67% the residue has no caking property. residues with similar extraction yields as shown in Figs. 3–
However, it is very interesting to note that for coking coal, 5. Very similar extraction yields (52.4% and 51.3%) can be
when the extraction yield gets to the maximum of 25.3% (in obtained for fat coal in the CS2/NMP mixed solvent with
1:1 by volume of the CS2/NMP mixed solvent), the residue NMP content of 90% and 20%, respectively, mentioned
still has caking property with the caking index of 19. This above. Fig. 3 shows the TG curves of the two residues with
may display that (1), not all of the caking constituents are similar extraction yields. It can be observed that the weight
soluble in the mixed solvent due to covalent bonded; and loss rate for the residue obtained from 90% NMP of the
(2), parts of the caking constituents are insoluble due to mixed solvent is less than that from 20% NMP of the mixed
strong associative interaction. We cannot distinguish them solvent, i.e. the former is heavier than the later. This may
in this case. suggest that the soluble constituents extracted from 90%
Fig. 2 shows that the caking index for the residues in the NMP of the mixed solvent are lighter compared to that
case of less than 50% of NMP contents is different from extracted from 20% NMP of the mixed solvent although
that for the residues in the case of more than 50% NMP their extraction yields are very similar. A similar result

110
NMP content is
140
100 less than 50%
90 NMP content is 120 fat coal residue from 90%
80 more than 50% NMP of the mixed solvent
Weight loss, %

70 100
60
G

50 fat coal 80 fat coal residue from 20%

40 NMP of the mixed solvent
30 60
20
10 coking coal 40
0
0 10 20 30 40 50 60 70 80 20
Extraction yield, wt%, daf 0 200 400 600 800
Temperature, °C
Fig. 2. Effects of extraction yields on the caking indexes of the residues
extracted in the CS2/NMP mixed solvents with different NMP mixed Fig. 3. TG curves of residues of fat coal from the CS2/NMP mixed solvent
ratios for fat coal and coking coal. with different NMP content.
1400 H. Shui et al. / Fuel 86 (2007) 1396–1401

120 Table 3
coking coal residure from 70% Peak height ratios from the FTIR spectra of fat coal
NMP of the mixed solvent Wavenumber 2920 cm1/3030 cm1 1690 cm1/3030 cm1
100
Residue from 8.5 5.0
Weight loss, %

coking coal residure from 40% 20% NMP content

80
NMP of the mixed solvent Residue from 7.8 3.3
90% NMP content
60

40
are shown in Table 3. The transmittances of the bands near
20 2920 cm1 and 1690 cm1 for the residue obtained by 90%
NMP of the mixed solvent are lower compared to the cor-
0 responding bands for the residue obtained by 20% NMP of
0 200 400 600 800
Temperature, °C the mixed solvent. The transmittance decrease in
2920 cm1 suggests decreasing of –CH2 side chain of the
Fig. 4. TG curves of residues of coking coal from the CS2/NMP mixed residue and this is consistent with the TG analysis above.
solvent with different NMP content. The transmittance decrease in 1690 cm1 may suggest
decreasing of oxygen group in the residue. This means that
much of the oxygen group can be extracted by 90% NMP
of the mixed solvent.
a

3.3. Effect of soluble constituents on the caking propensity

of coal
T%

TG and FTIR analyses show that the fat and coking

coal residues extracted from the CS2/NMP mixed solvent
with NMP content less than 50% have much of oxygen
groups, therefore they have lower caking indexes compared
4000.0 3000 2000 1500 1000 450.0 to those from NMP content more than 50% of the CS2/
NMP mixed solvent with similar extraction yields for the
cm-1
same coal. The result shows that soluble component has
Fig. 5. FTIR spectra of residues from the CS2/NMP mixed solvent with a great effect on the caking propensity of coal. The content
different NMP content: (a) fat coal residue from 20% NMP of the mixed of the constituents with suited molecular masses and low
solvent and (b) fat coal residue from 90% NMP of the mixed solvent. melting donor hydrogen rich species presented within the
coal structure dominates the development of plastic layer
when coal is heated to 370–400 °C. The lighter constituents
can be observed for coking coal as shown in Fig. 4. In cok- in coal, which contain much of hydrogen, are easy to
ing coal case, 70% NMP of the mixed solvent gives an become volatile materials released from coal macromole-
extraction yield of 18.8%, and the caking index of the res- cules before the plastic temperature of coal, resulting in
idue extracted is 41. However, when the NMP content the decrease of coking index of the coal due to the lack
decreases to 40% (less than 50%) in the mixed solvent, of hydrogen donating of coal structure. Nomura and
the extraction yield of the coking coal is 17.2%, a little Thomas [9] investigated the molecular structural changes
lower than 18.8%, but the caking index of the residue during the carbonization process by diffuse reflectance
extracted is 32, much smaller than 41. Still the weight loss infrared Fourier transform (DRIFT) spectroscopy. They
rate for the residue obtained from 70% NMP of the mixed found that the relative intensity of methylene groups
solvent is less than that obtained from 40% NMP of the (–CH2) decreased with increasing temperature in the ther-
mixed solvent. In order to understand the structural differ- moplastic temperature. In addition, the oxygen functional
ence, FTIR spectra were measured for the two residues of groups, mainly hydroxyl oxygen, are believed to be respon-
fat coal with similar extraction yields as shown in Fig. 5. sible for the generation of cross-linked chars. The deoxy-
Fig. 5 shows that FTIR spectra of the two residues are sim- genation at a given temperature is considered a highly
ilar, indicating their similar structure because they come significant prerequisite for the development of caking prop-
from the same coal with similar extraction yields. However, erty of coal [10]. In our previous work [6], we found that
a little subtle change can be observed from the FTIR spec- NMP cannot enter the inside of the network of coal, it
tra. The peak height ratios from the FTIR spectra based on can only extract the outside molecules of coal network
3030 cm1 attributed to aromatic C-H stretch vibration, structure. The CS2/NMP mixed solvent has lower viscosity;
which is believed to be unchanged for the two residues it can enter the inside of the network of coal and extract the
 H. Shui et al. / Fuel 86 (2007) 1396–1401 1401

soluble fractions to be inside the network. The CS2/NMP light constituents containing less of oxygen groups, result-
mixed solvent with NMP content less than 50% should ing in the decrease in caking indexes for the residues
have lower viscosity than that of the mixed solvent with obtained at the similar extraction yields compared to those
more than 50% of NMP, so it can extract the soluble con- of the CS2/NMP mixed solvents with NMP more than
stituent at the inside of the network of coal. This will cause 50%.
further aggregation of the heavier molecules left in the res-
idue [11], resulting in the decrease of the caking index of the Acknowledgments
residue. In addition, for the fat coal and coking coal used in
this study, much of the constituents with suited molecular This work was supported by the National Natural
masses and low melting donor hydrogen rich species and Scientific Foundation of China (20676001) and Natural
also lower content of oxygen functional groups, which Science Foundation of Anhui Province (050440301). The
are beneficial for the developing of caking property of coal, authors also appreciate the financial support rendered by
are existed in the inside of coal network macrostructure. innovative group of Anhui Province ‘‘Coal Resource Pro-
The CS2/NMP mixed solvent with NMP content less than cessing & Cleaning Utilization’’.
50% can extract much more of these constituents, which
are useful to the development of plastic layer of coal com-
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