 New Carbon†“ Silica Composite Adsorbents from Elutrilithe Xiaohu Deng, Yinghong Yue,

and Zi Gao1 Department of Chemistry, Fudan University, Shanghai 200433, People†™s

Republic of China Received October 15, 1997; accepted May 8, 1998 Carbon†“ silica
composite adsorbents with high surface area and pore volume were prepared from natural
elutrilithe.(Karbon Baru Karbon Adsorben dari Elutrilithe Xiaohu Deng, Yinghong Yue, dan Zi
Gao1 Departemen Kimia, Universitas Fudan, Shanghai 200433, Republik Rakyat China
Diterima pada tanggal 15 Oktober 1997; diterima 8 Mei 1998 Carbonâ ???? silika komposit
adsorben dengan luas permukaan yang tinggi dan volume pori dibuat dari elutrilithe alam).

 The elutrilithe was chemically activated with K2CO3 at 1123 K and then dis- solved in water.
The textural and adsorptive properties of the composite adsorbents can be adjusted by
varying the pH and concentration of the sol mixture and the gel aging temperature.
Composite adsorbents prepared at low concentration have high adsorption capacities for
both water (43.4%) and cyclohexane (32.0%), exceeding those of ordinary commercial silica
gel and active carbon. The adsorbents prepared at high concentration are more hydrophobic
in nature, with adsorption capacities for water and cyclohexane of 18.5 and 41.5%,
respectively. (• Elililitasnya diaktifkan secara kimiawi dengan K2CO3 pada 1123 K dan
kemudian diselesaikan dalam air. Sifat textural dan adsorptif dari adsorben komposit dapat
disesuaikan dengan memvariasikan pH dan konsentrasi campuran sol dan suhu penuaan
gel. Penyerap komposit yang dibuat pada konsentrasi rendah memiliki kapasitas adsorpsi
tinggi untuk kedua air (43,4%) dan sikloheksana (32,0%), melebihi kadar silika gel komersial
biasa dan karbon aktif. Adsorben yang dibuat pada konsentrasi tinggi lebih bersifat
hidrofobik, dengan kapasitas adsorpsi untuk air dan sikloheksana masing-masing 18,5 dan
41,5%).

 The composite adsorbents are resistant to repetitive adsorption and regeneration cycles. ©
1998 Academic Press Key Words: Carbon†“ silica adsorbent; elutrilithe; N2 adsorption
isotherm; pore distribution; adsorption capacities. 1. INTRODUCTION The development of
modern technology requires a continu- ous search for new adsorbents. Carbon†“ mineral
composite adsorbents can be considered as a new type of adsorbent, which may have
structures and adsorption properties different from the individual components (1, 2). In the
literature carbon†“ mineral composite adsorbents are prepared by mechanical mix- ing of
carbon and mineral adsorbents, addition of carbon particles to the mineral sol before
gelation, and carbonization of organic substances previously bonded to the mineral adsor-
bent (1). (• Penyerap komposit tahan terhadap siklus adsorpsi dan regenerasi yang
berulang. Â © 1998 Academic Press Key Words: Carbonâ ???? silika adsorben; elutrilithe;
Isoterm adsorpsi N2; distribusi pori; kapasitas adsorpsi 1. PENDAHULUAN Perkembangan
teknologi modern memerlukan pencarian baru untuk adsorben baru. Carbonâ ???? mineral
komposit adsorben dapat dianggap sebagai jenis adsorben baru, yang mungkin memiliki
struktur dan sifat adsorpsi berbeda dari masing-masing komponen (1, 2). Dalam literatur
carbonâ ???? adsorben komposit mineral dibuat dengan pencampuran mekanis dari
adsorben karbon dan mineral, penambahan partikel karbon ke sol mineral sebelum gelasi,
dan karbonisasi zat organik yang sebelumnya terikat pada adsorben mineral (1)).

 Elutrilithe is the unusable solid waste piled up outside many coal mines, contaminating the
environment seriously. It has been converted to active carbon adsorbents with high surface
area and porosity and low ash content by activation with KOH (3) or K2CO3 (4). However,
the yield is rather poor due to the low carbon content of elutrilithe.( • Elutrilithe adalah limbah
padat yang tidak dapat digunakan ditumpuk di luar banyak tambang batu bara, yang
mencemari lingkungan dengan serius. Telah dikonversi menjadi adsorben karbon aktif
dengan luas permukaan tinggi dan porositas dan kadar abu rendah dengan aktivasi dengan
KOH (3) atau K2CO3 (4). Namun, hasilnya agak buruk karena kandungan karbon rendah
dari elutrilithe.)
 Another method is to activate the carbon in elutrilithe with ZnCl2 to prepare a composite
adsorbent with adsorption properties similar to active carbon (5). In this paper, new
carbon†“ silica composite adsorbents with high adsorption capacities for both water and
organic com- pounds were prepared from elutrilithe and characterized. (• Metode lain adalah
mengaktifkan karbon dalam elaborasi dengan ZnCl2 untuk membuat adsorben komposit
dengan sifat adsorpsi yang serupa dengan karbon aktif (5). Dalam tulisan ini, adsorben
komposit silika karbon baru dengan kapasitas adsorpsi tinggi untuk air dan organik
ditambahkan dari elutrilithe dan karakteristiknya)

 The aim of the work is to provide a new route to utilize the coal waste for producing low-cost
adsorbent materials. 2. EXPERIMENTAL 2.1. Preparation of Adsorbents Black elutrilithe
from Shanxi province, China, was used as the starting material, which contains 29.1% C,
36.0% SiO2, 18.2% Al2O3, and 16.7% Ca, Mg, Fe, Mn, Cr, Ni, Ti, and Na oxides. The
elutrilithe was crushed and sieved to a particle size smaller than 100 mesh. Three grams of
elutrilithe was blended with 25% K2CO3 solution, dried in air at 383 K, preheated at 573 K in
flowing N2 for 3 h, and then heated to 1123 K at a rate of 20 K/min and held for 3 h. (•
Metode lain adalah mengaktifkan karbon dalam elaborasi dengan ZnCl2 untuk membuat
adsorben komposit dengan sifat adsorpsi yang serupa dengan karbon aktif (5). Dalam
tulisan ini, adsorben komposit silika karbon baru dengan kapasitas adsorpsi tinggi untuk air
dan organik ditambahkan dari elutrilithe dan karakteristiknya)

 The pyrolyzed product was cooled to room temperature, transferred to a beaker containing
10†“ 50 ml H2O, and stirred for 2 h. The pH of the system was adjusted to a specific value
by adding hydrochloric acid, and the gel was aged at 313†“ 373 K for 24 h. Then the gel
was washed free from chloride and dried at 383 K. 2.2. Characterization N2 adsorption
isotherms were measured on a Micromeritics ASAP 2000 instrument. The samples were
degassed at 573 K for more than 10 h before measurement. BET and Langmuir surface
areas were calculated from the N2 adsorption iso- therms, and the micropore and mesopore
volumes were deter- mined by t-plot and BJH methods (6). Carbon analysis was carried out
according to an ASTM method (7). 2.3. Adsorption Test The adsorption capacities of various
adsorbates were mea- sured in a flow system at 293 K under P/P0 5 0.5. The competitive
adsorption of water and heptane was carried out at 293 K in a flow-type apparatus described
in the literature (8). Hydrogen gas (15 cm3/min) was passed through a saturator held at 283
K and filled with a two-phase mixture of water and heptane. Breakthrough curves were
obtained by analyzing the adsorber effluents with an on-line gas chromatograph.1 To whom
correspondence should be addressed. JOURNAL OF COLLOID AND INTERFACE
SCIENCE 206, 52†“ 57 (1998) ARTICLE NO. CS985645 520021-9797/98 $25.00
Copyright © 1998 by Academic Press All rights of reproduction in any form reserved.
 3. RESULTS AND DISCUSSION 3.1. Effect of Preparative Conditions In our previous paper
(4), it was found that the optimal pyrolysis conditions for the activation of carbon in elutrilithe
were 1123 K, 3 h, and K2CO3/elutrilithe ratio 5 1. These conditions were taken for granted in
the preparation of carbon†“ silica composite adsorbents. Hence, in the present work only
the effects of pH, gel aging temperature, and concentration on the properties of the
adsorbents were studied. The results are summarized in Table 1. The sol mixture obtained
after pyrolysis with K2CO3 and dissolving in water was gelled under pH 20.2†“ 7.0 at 323
K. The carbon content of the samples increased from 17.8 to 36.6% as the pH changed from
7.0 to 20.2. Active carbon is a minor component of the composite material, so the textural
properties of the samples are principally dependent on the structure of the silica gel. As
shown in Table 1, the surface area and pore volume of the samples increased significantly at
lower pH. This has been explained in the literature (9) at higher pH the primary silica
particles grow before the gel is formed, which leads to a dry gel of lower specific surface
area and smaller pore volume. Figure 1 depicts the N2 adsorption and desorption isotherms
of the samples gelled at different pH. At pH 3.2†“ 7.0 the samples obtained are
 mesoporous materials with pores larger than 2 nm in diameter, whereas at pH # 2.0 the
samples have both micropores and mesopores as seen in Table 1. The rela- tion between
pH and the porosity of a silica gel is rather complicated as described in the literature (9). The
change in pore volume with pH for our samples is consistent with the result of Okkerse (9).
The increase in microporosity and/or mesoporosity of the samples made at pH # 2.0 can be
ex- plained on the basis that the condensation rate is low and the silica particle size in the
gel is smaller at lower pH, so the coalescence factor is greater and the gel is mechanically
stron- ger and more resistant to shrinkage upon drying. The N2 adsorption isotherms of
samples aged at different temperatures under pH 0 are shown in Fig. 2. It is obvious that the
pore diameter and the total pore volume of the samples increase as the temperature is
raised from 313 to 373 K, because higher aging temperature facilitates the formation of a gel
network with larger elementary particles. The surface area of the samples is in the order CS-
4 . CS-7 . CS-8 . CS-6. It varies with temperature irregularly, because the surface area of a
porous material increases with an increase in pore volume but decreases with an increase in
pore diameter. The concentration of the sol mixture also affects the textural properties of the
samples, as shown in Fig. 3 and Table 1. Diluting the sol mixture reduces the rate of
condensation and favors the formation of smaller silica particles, but it retards the gelling
process. These two factors are interrelated, so the TABLE 1 Effect of Preparative Conditions
on the Properties of the Composite Adsorbents Sample pH Aging temp. (K) H2O (ml)
Surface area (m2/g) Pore volume (cm3/g) Adsorption capacity (wt%) Carbon (m%)BET
Langmuir ,2 nm 2†“ 50 nm .50 nm Total AH2O AC6H12 CS-1 7.0 323 10 236 321 0 0.286
0.061 0.347 13.0 12.8 17.8 CS-2 3.2 323 10 286 389 0.009 0.230 0.009 0.248 16.8 12.9
19.8 CS-3 2.0 323 10 482 652 0.125 0.157 0.011 0.293 18.0 12.8 23.8 CS-4 0 323 10 791
1080 0.186 0.263 0.009 0.458 26.3 20.6 28.1 CS-5 20.2 323 10 780 1073 0.070 0.492 0.006
0.568 20.6 29.8 36.6 CS-6 0 313 10 569 768 0.170 0.133 0.009 0.312 23.9 17.0 27.3 CS-4 0
323 10 791 1080 0.186 0.263 0.009 0.458 26.3 20.6 28.1 CS-7 0 353 10 771 1062 0.060
0.496 0.018 0.574 43.4 32.0 22.9 CS-8 0 373 10 684 942 0 0.796 0.017 0.813 30.8 33.7
29.9 CS-9 0 353 50 727 1001 0.030 0.530 0.036 0.596 16.8 37.1 39.5 CS-10 0 353 30 698
963 0.013 0.635 0.018 0.666 18.5 41.5 38.5 CS-11 0 353 20 720 984 0.112 0.348 0.020
0.480 26.8 31.7 33.4 Silica gel-7 0 353 10 662 911 0.028 0.538 0.016 0.582 21.9 27.6 †”
Silica gel-10 0 353 30 713 986 0.054 0.448 0.005 0.507 23.2 29.8 †” Silica gel-C †”
†” †” 591 825 0 0.640 0 0.640 24.1 31.1 †” Carbon-E †” †” †” 1056 1435
0.269 0.336 0.025 0.630 11.7 40.8 †” Carbon-C †” †” †” 1013 1349 0.418 0.062 0
0.480 15.5 24.2 †” 53CARBON†“ SILICA ADSORBENTS
 variation in the textural properties of the samples with concen- tration is fluctuated. The
adsorption capacities of the composite materials ob- tained under different preparative
conditions for water and cyclohexane, as a representative of organic nonpolar com- pounds,
were measured and listed in Table 1. The composite carbon†“ silica adsorbents adsorb
appreciable amounts of water and cyclohexane at relative vapor pressures of 0.5 and 293 K.
In general, the uptake of water and cyclohexane increases with an increase in surface area
and pore volume of the adsorbents, and the ratio of AC6H12 to AH2O increases with the
carbon content in the composite adsorbents. Only in a few cases does the data diverge
somewhat from this main trend, probably due to some unidentified variations of adsorbent
pore structure and surface properties with change in preparative conditions. CS-7 and CS-8
in Table 1 are good multifunctional adsorbents whose adsorption capacities for both water
and cyclohexane exceed 30 wt%. On the other hand, CS-9 and CS-10 are more or less
hydrophobic adsorbents with a cyclohexane uptake higher than 37 wt% and a AC6H12 to
AH2O ratio greater than 2. 3.2 Properties of the Carbon†“ Silica Adsorbents The N2
adsorption isotherms of CS-7 and CS-10 are com- pared with the single constituents
prepared from elutrilithe under the same conditions in Fig. 4. Silica gel-7 and silica TABLE 2
Adsorption of Various Compounds on the Adsorbents Adsorbate Capacity (wt%) Silica gel-C
Carbon-C CS-7 CS-10 H2O 24.1 15.5 43.4 18.5 C6H12 31.1 24.2 32.0 41.5 CH3COCH3
38.4 27.4 48.7 42.9 C2H5OH 30.3 32.0 28.8 24.8 CH2Cl2 65.1 57.9 62.2 54.8 CCl4 66.1
 55.9 65.7 56.3 C6H6 37.6 43.9 37.6 33.4 C6H5CH3 50.0 35.5 41.0 37.3 C5H5N 41.4 32.1
48.7 43.2 FIG. 1. N2 adsorption isotherms of samples prepared at different pH. (a) CS-1, (b)
CS-2, (c) CS-3, (d) CS-4, and (e) CS-5. FIG. 2. N2 adsorption isotherms of samples
prepared at different temper- atures. (a) CS-6, (b) CS-4, (c) CS-7, and (d) CS-8. 54 DENG,
YUE, AND GAO
 gel-10 were prepared from elutrilithe precalcined at 773 K in air for 4 h to burn off the
carbonaceous material. Carbon-E was prepared from elutrilithe by pyrolysis with K2CO3 at
1123 K for 3 h and then treated with 2 mol/l HNO3 and 5% NaOH as in the literature (4). The
textural and adsorption properties of the silica gels and active carbon are given in Table 1.
The experimental and calculated isotherms of CS-7 lie in between the isotherms of carbon-E
and silica gel-7 as expected, and the experimental isotherm of CS-7 lies above the
calculated iso- therm at higher relative pressure, showing that microporosity of the composite
is not influenced by mixing but mesoporosity is slightly increased. This increase in
mesoporosity can be explained as a result of the fixation of small carbon particles in the
interstices of silica gel and the precipitation of silica gel in the wider pores of carbon (10).
The experimental isotherm of CS-10 lies much lower than the calculated isotherm and
almost overlaps on the isotherm of silica gel-10 at lower relative pressure, whereas at higher
relative pressure the isotherm rises abruptly, implying that mixing the two components
reduces microporosity and increases mesoporosity in the composite. This suggests that
some of the micropores of carbon are blocked upon gelation at low concentration. The
increase in mesoporosity for CS-10 bears the same reason as that for CS-7, but the low sol
concentration in this case enlarges the inter- mixing effect of the two components. The
adsorption of various common adsorbates on CS-7, CS-10, commercial silica gel-C, and
commercial active car- bon-C is summarized in Table 2. The uptakes of water, cyclohexane,
acetone, and pyridine on CS-7 are larger than those on commercial silica gel and carbon,
whereas the up- takes of the other adsorbates on CS-7 are close to those on the two
commercial adsorbents. The adsorptive properties of CS-10 are similar to those of CS-7,
except that its uptake of water is much smaller. The above results show that the com- posite
adsorbents prepared from elutrilithe not only have high adsorption capability but also are
characterized by better ad- sorption than the individual components of the adsorbents for
some adsorbates. TABLE 3 Effect of Regeneration on the Adsorbents Sample Surface area
(m2/g) Pore volume (cm3/g) Adsorption capacity (wt%) BET Langmuir ,2 nm 2;50 nm .50 nm
Total AH2O AC6H12 CS-7 771 1062 0.060 0.496 0.018 0.574 43.4 32.0 CS-7a 593 807
0.132 0.220 0.023 0.375 27.6 22.0 CS-10 698 963 0.013 0.635 0.018 0.666 18.5 41.5 CS-
10a 701 961 0.029 0.582 0.026 0.637 14.1 36.3 Silica gel-C 591 825 0 0.640 0 0.640 24.1
31.1 Silica gel-Ca 556 773 0 0.506 0.001 0.507 15.4 30.3 Carbon-C 1013 1349 0.418 0.062
0 0.480 15.5 24.2 Carbon-Ca 922 1224 0.392 0.044 0 0.436 10.4 24.0 a After regeneration
10 times at 383 K for 10 h. FIG. 3. N2 adsorption isotherms of samples prepared at different
concen- trations. (a) CS-11, (b) CS-10, (c) CS-9. 55CARBON†“ SILICA ADSORBENTS
 The hydrophobic and hydrophilic surface properties of the adsorbents were characterized by
the competitive adsorption of heptane and water from the gas phase (8). Figure 5 depicts the
breakthrough curves in the competitive adsorption on the ad- sorbents. In the diagrams, P0
and P denote the partial pressure of heptane or water in the initial and effluent gas mixtures,
respectively. Very pronounced differences were observed in the breakthrough curves of
carbon-C and silica gel-C. On carbon-C the breakthroughs of both heptane and water occur
almost simultaneously, showing that carbon-C has both hydro- phobic and hydrophilic
properties. However, silica gel-C is clearly identified as more hydrophilic, because not only is
water removed from the gas stream for a much longer time but also the P0/P of heptane
rises above 1 during the course of adsorption due to the displacement of the adsorbed
heptane by water. CS-7 and CS-10 resemble silica gel in their surface properties, but CS-10
is somewhat more hydrophobic, which is consistent with the results of the above adsorption
capacity measurements. Similar to pure silica gel, the surface of the composite adsorbents is
abundant in terminal hydroxyl groups responsible for their hydrophilicity in adsorption (2). A
 higher proportion of carbon in CS-10 causes a small reduction in surface hydroxyl groups,
and hence a slight increase in hydro- phobicity. The effect of heat treatment or regeneration
on the adsor- bents was also studied. The adsorbents were saturated with cyclohexane and
water vapors in sequence at ambient temper- ature, and then heated at 383 K for 10 h to
recover. This adsorption and regeneration process was repeated 10 times for each
adsorbent. The textural and adsorption properties of the adsorbents before and after
regeneration 10 times are compared in Table 3. The loss in surface area and pore volume of
CS-7 after regeneration is more distinct than all the others, indicating that sintering takes
place more readily in the adsorbent. In contrast, CS-10 is more thermally stable. Its surface
area re- mains about the same after regeneration, and its pore volume only decreases
slightly. It should be noted that due to its larger pore volume the adsorption capacities of
water and cyclohex- FIG. 4. N2 adsorption isotherms of the composite adsorbents and their
constituents. (a) Carbon-E, (b) CS-7(exp), (c) CS-7(cal), (d) silica gel-7, (e) CS-10(exp), (f)
CS-10(cal), (g) silics gel-10. 56 DENG, YUE, AND GAO
 ane on CS-10 after regeneration are still considerably higher than those on active carbon,
and at the same time it exceeds silica gel in its cyclohexane uptake. On the other hand, the
water uptake of CS-7 after regeneration remains the highest among all the adsorbents
because of its hydrophilic surface and microporosity. 4. SUMMARY From the above results,
we are convinced that elutrilithe can be utilized as a raw material for producing low-cost
carbon- silica composite adsorbents with high adsorption capacity for both water and organic
compounds. The surface and textural properties of the composite adsorbents can be
adjusted by varying the preparative conditions, and the intimate mixing of the two
constituents in the interstices of each other may create new mesoporoity. The composite
adsorbents prepared under appropriate conditions have adsorptive features superior to the
pure constituents and may be used for defined purposes. REFERENCES 1. Leboda, R.,
Mater. Chem. Phys. 31, 243 (1992). 2. Leboda, R., Mater. Chem. Phys. 34, 123 (1993). 3.
Hu, Z. H., and Vansant, E. F., Carbon 33, 1293 (1995). 4. Deng, X. H., Yue, Y. H., and Gao,
Z., J. Colloid Interface Sci. 192, (1997). 5. Hu, Z. H., and Vansant, E. F., J. Colloid Interface
Sci. 176, 422 (1995). 6. Gregg, S. J., and Sing, K. S. W., in †œAdsorption, Surface Area
and Porosity.†• Academic Press, London, 1982. 7. †œAnnual Book of ASTM
Standards,†• Part 30, D2866-70, 1978. 8. Weitkamp, J., Kleinschmit, P., Kiss, A., and
Berke C. H., in †œProceedings 9th Inter. Zeol. Conf.†• (R. von Ballmoos et al., Eds.),
p.79. Butterworth- Heinemann, Montreal, 1992. 9. Iler, R. K., in †œThe Chemistry of
Silica.†• John Wiley & Sons, New York, 1979. 10. Bansal, R. C., and Dhami, T. L., Ind. J.
Chem. 21A, 105 (1982). FIG. 5. Breakthrough curves in the competitive adsorption of
heptane/water vapors on the adsorbents. (F) water, and (n) heptane.
57CARBON†“ SILICA ADSORBENTS

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