Characteristics on Chemical Activation and VOCs Adsorption ...
14
Clean Technol., Vol. 23, No. 4, December 2017, pp. 364-377 * To whom correspondence should be addressed. E-mail: [email protected]; Tel: +82 51 510 2417; Fax: +82 51 583 0559 doi: 10.7464/ksct.2017.23.4.364 pISSN 1598-9712 eISSN 2288-0690 This is an Open-Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License (http://creativecommons.org/licences/ by-nc/3.0) which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited. 청정생산공정기술 활성탄 제조시 유 ․ 무연탄 혼합에 따른 화학적 활성화 및 휘발성유기화합물 흡착 특성 조준형 1 , 강성규 2 , 강민경 3 , 조국 3 , 오광중 3, * 1 부산대학교 창의적 해양항만도시 인프라 저영향개발 및 관리체계 구축사업단 46241 부산광역시 금정구 부산대학로 63번길 2 2 부산대학교 사회환경시스템공학과 46241 부산광역시 금정구 부산대학로 63번길 2 3 한국폴리텍Ⅶ대학 에너지환경과 51518 경상남도 창원시 성산구 외동반림로 51-88 (2017년 10월 25일 접수; 2017년 11월 5일 수정본 접수; 2017년 11월 5일 채택) Characteristics on Chemical Activation and VOCs Adsorption of Activated Carbon according to Mixing Ratio of Anthracite and Lignite Joon-Hyung Cho 1 , Sung-Kyu Kang 2 , Min-Kyoung Kang 3 , Kuk Cho 3 , and Kwang-Joong Oh 3, * 1 Division of Creative Low Impact Development and Management for Ocean Port City Infrastructures, Pusan National University 2, Busandaehak-ro 63beon-gil, Geumjeong-gu, Busan, 46241, Republic of Korea 2 Department of Civil and Environmental Engineering, Pusan National University 2, Busandaehak-ro 63beon-gil, Geumjeong-gu, Busan, 46241, Republic of Korea 3 Department of Environmental Chemistry, Korea Polytachnic VII Collage 51-88, Oedongballim-ro, Seongsan-gu, Changwon-si, Gyeongsangnam-do, 51518, Republic of Korea (Received for review October 25, 2017; Revision received November 5, 2017; Accepted November 5, 2017) 요 약 본 연구에서는 활성탄 원료로서 국내산 무연탄의 낮은 비표면적을 향상시키기 위해 유·무연탄 혼합에 따른 화학적 활성화 및 휘발성유기화합물 흡착특성 연구를 수행하였으며, 이를 위해 원료 물성, 활성탄 제조공정별 특성, 제조 활성탄의 휘발성 유기화합물 흡착성능이 분석되었다. 실험결과, 삼성분 항목 중 높은 회분함량과 기준을 초과한 납, 비소 중금속이 국내산 원 료의 단점으로 나타났다. 단점 개선을 위해 유·무연탄을 혼합하고, 전처리, 활성화, 세척, 조립 공정의 최적 조건을 도출하여 비표면적 1,154 ~ 1,420 m 2 g -1 의 중간세공이 발달한 소수성의 활성탄을 제조할 수 있었으며, 모든 품질규격기준을 만족하였 고, 상용활성탄과 유사한 물리화학적 특성을 나타내었다. 벤젠, 자일렌, 톨루엔 흡착에 상용 성능을 위한 원료 혼합조건은 최소 5,640 kcal kg -1 이상의 발열량이 필요하며, 자일렌 > 톨루엔 > 벤젠의 순서로 흡착성능이 우수한 것으로 보아 상대적으 로 분자량이 크고 소수성이 강한 휘발성 유기화합물에 대하여 우수한 흡착성능을 가지는 것으로 나타났다. 주제어 : 활성탄, 화학적 활성화, 무연탄, 유연탄, 휘발성 유기화합물 Abstract : In this study, to improve the low surface area of domestic anthracite as raw materials of activated carbon, characteristics on chemical activation and VOCs adsorption of activated carbon according to mixing ratio of anthracite and lignite. For these, properties of raw materials, parameter characteristics of preparation processes for activated carbon, and VOCs adsorption characteristic of the prepared activated carbon are analyzed. The experimental results showed that, the domestic anthracite had disadvantages of high contents for ash and lead, arsenic, which were exceeded for the heavy metal limits, in the properties of raw materials. To improve these diadvantages, using the mixing ratio of anthracite and lignite, and the optimum conditions for pretreatment, activation, washing, and pellitization process, the activated carbon had a range of BET (Brunauer-Emmett-Teller) surface area of 1,154 ~ 1,420 m 2 g -1 with mesopore development and hydrophobic surface property. The carbons were satisfied 364
Transcript of Characteristics on Chemical Activation and VOCs Adsorption ...
03-KC2017-049 Rev[1] File[1398].hwpClean Technol., Vol. 23, No. 4,
December 2017, pp. 364-377
* To whom correspondence should be addressed. E-mail: [email protected]; Tel: +82 51 510 2417; Fax: +82 51 583 0559
doi: 10.7464/ksct.2017.23.4.364 pISSN 1598-9712 eISSN 2288-0690 This is an Open-Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License (http://creativecommons.org/licences/ by-nc/3.0) which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.
1, 2, 3, 3, 3,* 1
46241 63 2 2
46241 63 2 3
51518 51-88
(2017 10 25 ; 2017 11 5 ; 2017 11 5 )
Characteristics on Chemical Activation and VOCs Adsorption of Activated Carbon according to Mixing Ratio of Anthracite and Lignite
Joon-Hyung Cho1, Sung-Kyu Kang2, Min-Kyoung Kang3, Kuk Cho3, and Kwang-Joong Oh3,* 1Division of Creative Low Impact Development and Management for Ocean Port City Infrastructures, Pusan National University
2, Busandaehak-ro 63beon-gil, Geumjeong-gu, Busan, 46241, Republic of Korea 2Department of Civil and Environmental Engineering, Pusan National University
2, Busandaehak-ro 63beon-gil, Geumjeong-gu, Busan, 46241, Republic of Korea 3Department of Environmental Chemistry, Korea Polytachnic VII Collage
51-88, Oedongballim-ro, Seongsan-gu, Changwon-si, Gyeongsangnam-do, 51518, Republic of Korea
(Received for review October 25, 2017; Revision received November 5, 2017; Accepted November 5, 2017)
·
, , ,
. , ,
. · , , , ,
1,154 ~ 1,420 m2 g-1 ,
, . , ,
5,640 kcal kg-1 , > >
.
: , , , ,
Abstract : In this study, to improve the low surface area of domestic anthracite as raw materials of activated carbon, characteristics on chemical activation and VOCs adsorption of activated carbon according to mixing ratio of anthracite and lignite. For these, properties of raw materials, parameter characteristics of preparation processes for activated carbon, and VOCs adsorption characteristic of the prepared activated carbon are analyzed. The experimental results showed that, the domestic anthracite had disadvantages of high contents for ash and lead, arsenic, which were exceeded for the heavy metal limits, in the properties of raw materials. To improve these diadvantages, using the mixing ratio of anthracite and lignite, and the optimum conditions for pretreatment, activation, washing, and pellitization process, the activated carbon had a range of BET (Brunauer-Emmett-Teller) surface area of 1,154 ~ 1,420 m2 g-1 with mesopore development and hydrophobic surface property. The carbons were satisfied
364
365
with the quality standard for granular activated carbon, and had similar physicochemical properties with the commercial activated carbon. The minimum mixing condition for commercial VOCs activated carbon performance must have the caloric value of above 5,640 kcal kg-1, and the carbon had higher adsorption capacity with order of xylene > toluene > benzene according to more higher molcular weight and hydrophobic property.
Keywords : Activated carbon, Chemical activation, Anthracite, Lignite, Volatile organic compounds
1.
,
. , , ,
,
[1]. 2015
, , ,
[2],
,
,
. ,
50 ,
10 1,000
· ,
19 ~ 36% [1]. ( , , ) 50,767
99.6%
, , ,
79.8%
[3].
, , , , , ,
4, 5,000
[4]. 3 M, DuPont
,
Calgon, Norit
[5].
, 15 [6], , ,
, 20 .
, 24,300/
38%
, 2014 115,429 2006 13%
[7].
. ,
, , ,
,
.
2 . ,
, 936 2,381
94,600 ~ 197,490
[8,9].
(62 ~ 70%) (33~35%)
.
.
2 ,
,
. ,
, (phosphoric acid), (zinc chloride), (potassium carbonate), (sodium hydroxide), (potassium hydro- xide) [12-14].
, ,
, , ,
[10-12].
,
, Kong et al. [13]
, 920 m2 g-1 . Kim,
366
Figure 1. Schematic diagram of activation process reactor.
et al. [14] 2 , 900 ~ 1,000 m2 g-1 .
1,000 m2 g-1
.
, Yoon et al. [15]
1,014 ~ 1,093 m2 g-1
, Kim et al. [16]
1,039 ~ 1,232 m2 g-1
, Choi et al. [17] ·
1,084 m2 g-1 .
,
,
.
, , ,
, , ,
,
BET (Brunauer–Emmett–Teller) ,
, FTIR (Fourier Transform Infrared) .
.
2.
2.1.
, .
8 ~ 35 mesh .
(Nitric acid, Samchun, KOR, purity 60%), (Hydro- chloric acid, Samchun, KOR, purity 35 ~ 37%), (Phophoric acid, Samchun, KOR, purity 85%), (Sulfuric acid, Junsei, JPN, purity 95%) ,
(Potassium hydroxide, Samchun, KOR, purity 85%) . CMC (Car- boxylmethyl cellulose sodium salt, Samchun, KOR), PVA (Polyvinyl alcohol, Samchun, KOR), (Starch, Samchun, KOR), (Gum arabic, Samchun, KOR) .
2.2.
, , , , , .
(OV-11/CTB-10, Jelo Tech, KOR) -0.1 MPa, 90 , 24 h
,
(SH-820F, Seyoung Scientific, KOR)
, (0.5 ~ 16 M)
(1 ~ 5 mL g-1), (6 ~ 48 h) .
367
Table 1. Proximate, element, caloric value, heavy metal analysis for low-grade anthracite, anthracite, and ligniet as raw material of activated carbon
Items Analyzed items Unit
Ash % 43.0 31.13 14.55 - Fixed carbon % 49.10 60.99 76.28 -
Element
C % 26.20 62.50 80.1 - H % 1.10 0.80 3.00 - O % 1.10 2.00 4.30 - N % 0.40 0.40 1.70 - S % 0.08 0.24 0.43 - Cl % 0.08 0.01 0.00 -
Caloric value
Lower heating value
Heavy metal
Hg mg kg-1 0.00 0.04 0.00 - Cd mg kg-1 0.00 0.61 1.62 1 Pb mg kg-1 39.90 33.90 9.00 10 As mg kg-1 2.20 7.60 0.00 2 Cr mg kg-1 33.20 57.80 47.3 - Co mg kg-1 5.50 8.20 12.9 - Cu mg kg-1 5.20 28.60 0.0 - Mn mg kg-1 24.50 74.50 693 - Ni mg kg-1 11.40 45.30 31.70 - Tl mg kg-1 0.00 0.00 0.00 - V mg kg-1 47.80 20.10 7.40 -
(25 ~ 90 ) (6 ~ 48 h) ,
115 . 24 h . Figure 1 (STF-15/
75/610, Carbolite Ltd., UK) , (Euro- therm 2408CP, Carbolite Ltd., UK) 1,500
, 16
,
. 1,000 mm, 500 mm , 6
. 1,000 mm, 50 mm, 5 mm,
, , 0.5 ~ 5.0 L min-1
.
20 ,
,
. , ,
30 g
,
99.9% (0.5 ~ 2 L min-1)
10 min-1 (700 ~ 900 )
, (2 ~ 5 h)
. ,
,
.
(0.1 ~ 5 M) (1 ~ 4 mL g-1), (0.5 ~ 4 h)
, pH
, ,
-0.1 MPa, 90 , 24 h .
, (5 ~ 15%)
-0.1 MPa, 90 , 24 h .
BET , , FTIR . BET
(Micromeritics ASAP 2020, USA)
90 , 10 min-1, 350 , 4 h
-196 ,
0.05 ~ 0.15 P/P0 5
0.9999 , C . KSM 1802 , , , , FTIT
(IRAffinity-1 Shimadzu, Japan) .
(ASTM D6646-03)
,
,
(50 ppm), (5,000 ppm),
, , (10,050 ppm)
,
(ppbRAE 3000, REA systems, Inc., USA)
. 3
.
368
Figure 2. BET surface area and ash content of activated carbon according to (a) pretreatment agents, (b) HNO3 concentration, (c) HNO3/ anthracite ratio, and (d) pretrement time in pretreatment process.
, , ,
,
. , (%) (8.9) > (6.1)
(6.1)
, (%)
(43.0) > (31.1) > (14.6)
11.9 ~ 28.4% , (%)
(76.3) > (61.0) > (49.1)
.
,
,
. , C (%) (80.1) > (62.5) >
(26.2)
, H (%) 3%
. O (%) 5%
, N, S, Cl 0.5%
. (kcal kg-1) , (7,086) > (5,162) > (2,360) .
7,400 kcal kg-1 30.2 ~ 68.1%
, C
. , (mg kg-1) (802.9) >
(276.7) > (169.7) , Pb
(mg kg-1) (39.9) > (33.9) > (9.0) 10 mg kg-1 , As (mg kg-1) (7.6) >
(2.2) > (0.0)
2 mg kg-1 , Cd (mg kg-1) (1.62) > (0.61) > (0.0)
1 mg kg-1 .
, Cd, Pb, As 3
.
3.2.
.
,
.
3.2.1.
Figure 2 (a) , (b)
369
Table 2. Coagulation properties of anion and cation in aqueous solution
Anion→ Cl- NO3 - SO4
Cation↓
Ag+ I S S I Hg+ I S VSS I Ba2+ S S I I Ca2+ S S VSS I Cu2+ S S S I Cd2+ S S S I Co2+ S S S I Fe2+ S S S I Hg2+ S S VSS I Mg2+ S S S I Mn2+ S S S I Ni2+ S S S I Pb2+ I S I I Sr2+ S S VSS I Zn2+ S S S I Al3+ S S S I As3+ S X X X Cr3+ S S S I Fe3+ S S S I V3+ S S S I
Note : S = soluble (>5000 mg L-1), SS = slightly soluble (2000-5000 mg L-1), VSS = very slightly soluble (20-2000 mg L-1), I = insoluble (< 20 mg L-1), X = not compound.
, (c) , (d)
25 24 h, ,
900 , 4 h, 1 L min-1, (KOH/ anthracite, wt% wt%-1) 4 , 0.5 M , , 4 mL g-1, 2 h
. Figure 2(a) , (m2
g-1) (1685.4) > (539.9) > (210.4) > (39.7) .
(SiO2) 49 ~ 57%, (Al2O3) 27 ~ 31%, (Fe2O3) 4 ~ 10%, (CaO) 2 ~ 6%, (MgO) 0.4 ~ 1.3%
[18]. Equation (1)~(13)
, ,
[19-23], Table 2
[24,25]
, , , . ,
, , ,
.
.
Al2O3(s) + 6HCl(aq) → 2AlCl3(aq) + 3H2O (5)
Fe2O3(s) + 6HCl(aq) → 2FeCl3(aq) + 3H2O (6)
CaO(s) + 2HCl(aq) → CaCl2(aq) + H2O (7)
Al2O3(s) + 3H2SO4(aq) → Al2[SO4]3(aq) + 3H2O (8)
Fe2O3(s) + 3H2SO4(aq) → Fe2[SO4]3(aq) + 3H2O (9)
CaO(s) + H2SO4(aq) → CaSO4(s) + H2O (10)
Al2O3(s) + H3PO4(aq) → 2Al[PO4](s) + 3H2O (11)
Fe2O3(s) + H3PO4(aq) → 2Fe[PO4](s) + 3H2O (12)
3CaO(s) + 2H3PO4(aq) → Ca3[PO4]2(s) + 3H2O (13)
(%) , (28.1) >
(26.8) > (22.5) > (21.6) 3
.
.
. Figure 2(b) ,
(m2 g-1) 16 M (1830.0) > 10 M (1829.9) > 5 M (1565.4) > 1 M (1194.5) > 0.1 M (1027.0)
, 10 M .
,
.
, 0.5 M (28.6) > 1 M (27.2) > 5 M (23.8) > 10 M (21.6) 16 M (21.6)
.
10 M .
370
Figure 3. BET surface area of activated carbon according to (a) mixing temperature, and (b) mixing time in mixing process.
Figure 2(c) , (m2 g-1) 5 mL g-1 (1832.1) > 4 mL g-1 (1829.9) > 3 mL g-1 (1687.3) > 2 mL g-1 (1431.8) > 1 mL g-1 (423.8)
, 4 mL g-1
.
,
. (%) , 1 mL g-1 (31.55) > 2 mL g-1 (25.0) > 3 mL g-1 (22.5) > 4 mL g-1 (21.6) 5 mL g-1 (21.6) .
4 mL g-1 . Figure 2(d) , (m2
g-1) 48 h (1708.7) 24 h (1685.4) 12 h (1685.4) > 6 h (1156.5) 6 h 12 h . 12 h ,
.
(%) 6 h (30.8) > 12 h (21.6) 24 h (21.5) 48 h (21.3) .
12 h .
3.2.2.
Figure 3 (a) , (b)
10 M , 4 mL g-1, 12 h,
, 900 , 4 h, 1 L min-1, (KOH/anthracite, wt% wt%-1) 4
, 0.5 M , , 4 mL g-1, 2 h .
Figure 3(a) , (m2 g-1) 90 (1685.4) > 55 (1675.2) > 25 (1662.8)
.
,
1.4%
.
25 . Figure 3(b) , (m2 g-1)
48 h (1686.2) > 24 h (1685.4) > 12 h (1495.4) > 6 h (1256.5) , 24 h .
24 h
, 24 h .
3.2.3.
Figure 4 (a) , (b) , (c) , (d)
Figure 4(d)
.
10 M , 4 mL g-1, 12 h, 25 24 h,
0.5 M , , 4 mL g-1, 2 h
. Figure 4(a) , (KOH/anthracite,
wt% wt%-1) (m2 g-1) 4 (1829.9) > 5 (1435.5) > 3 (1329.3) > 2 (791.1)
4
,
. Equation (14) C KOH
1 : 3 [11,26,27],
1 : 4
,
.
4
.
371
Figure 4. BET surface area of activated carbon according to (a) KOH/anthracite ratio, (b) activation temperature and time, (c) nitrone flow rate, and (d) caloric value in activation process [note : the analysis results for ash and carbon content were included in Figure 4(d)].
6KOH + 2C → 2K + 3H2 + 2K2CO3 (14)
Figure 4(b) , 4 h (m2 g-1) 900 (1829.9) > 800 (1740.5) > 700 (1500.5)
, 900 . Equation (14)
Equation (15) ~ (18) 800
[27],
. 900
(m2 g-1) 4 h (1829.9) > 3 h (1685.4) > 5 h (1450.5) > 2 h (1136.4) > 1 h (1025.4)
4 h ,
. 4 h
.
900 , 4 h .
K2CO3 → K2O + CO2 (at 700 ~ 800 ) (15)
CO2 + C → 2CO (16)
Figure 4(c) ,
(m2 g-1) 2.0 L min-1 (1875.9) 1.5 L min-1 (1864.5)
1.0 L min-1 (1829.9) > 0.5 L min-1 (1155.4) 0.5 L min-1
1.0 L min-1
.
, , .
1.0 L min-1 . Figure 4(d) ,
(m2 g-1) 7,086 kcal kg-1 (2073.1) > 6,124 kcal kg-1 (1915.0) > 5,162 kcal kg-1 (1,685.4) > 3,761 kcal kg-1
(1,230.6) > 2,360 kcal kg-1 (633.5)
, . 1,000 m2 g-1
3,300 kcal kg-1 , 39% .
3.2.4.
Figure 5 (a) , (b) , (c) , (d)
372
Figure 5. BET surface area of activated carbon according to (a) washing agents, (b) HCl concentration, (c) HCl/anthracite ratio, and (d) washing time in washing process.
Figure 6. BET surface area and hardness of activated carbon according to (a) binder kinds, and (b) binder content in pelletization process.
HW (hot water), CW (cold water) . 10 M ,
4 mL g-1, 12 h,
25 24 h, ,
900 , 4 h, 1 L min-1, (KOH/anthracite, wt% wt%-1) 4 .
Figure 5(a) , (m2 g-1) HCl-HW-CW (1829.9) HW-CW (425.3) > CW (280.8)
1,400 m2 g-1
. Equation (14) ~ (18)
, ,
,
. ,
85
.
--
.
Figure 6 (a) , (b)
373
Table 3. BET surface area, pore volume, and average pore width of pelletized activated carbons
Sample Low-grade anthracite
Low-grade anthracite + Anthracite
activated carbon
BET surface area (m2 g-1) 433.8 842.7 885.1 1154.2 1191.9 1419.7 1522.3
Micropore area (m2 g-1) 367.4 453.3 437.7 758.8 598.6 827.5 1314.2
External area (m2 g-1) 66.5 389.4 447.4 395.4 593.3 592.2 208.1
Total pore volume (cm3 g-1) 0.242 0.523 0.593 0.608 0.654 0.753 0.692
Micropore volume (cm3 g-1) 0.158 0.208 0.205 0.326 0.271 0.361 0.55
Mesopore volume (cm3 g-1) 0.084 0.314 0.388 0.282 0.383 0.392 0.142
Average pore width () 22.3 24.8 26.7 21.0 21.9 21.2 18.2
10 M , 4 mL g-1, 12 h, 25 24 h,
, 900 , 4 h, 1 L min-1, (KOH/anthracite, wt% wt%-1) 4,
0.5 M , , 4 mL g-1, 2 h
. Figure 6(a) ,
(m2 g-1) CMC (1250.4) > Starch (1173.6) > Guargum (1120.9) > PVA (1040.7) . Lozano-Castello et al. [28] CMC
, PVA
.
. (%) , CMC (94) > PVA (67) > Guargum (51) > Starch (36)
, KSM 1802 90%
-25.8% , CMC
.
CMC , CMC
. Figure 6(b) , (m2
g-1) 0% (1685.5) > 5% (1541.1) > 10% (1379.9) > 15% (1250.4)
. (%)
, 15% (94) > 10% (84) > 5% (77) 0% (10) 5% , 5% 15%
. KSM 1802
90%
15% .
3.4.
,
BET , , FTIR .
3.4.1. BET
BET
(m2 g-1) , Commercial AC (1522.3) > Lignite (1419.7) > Anthracite + Lignite (1191.9) > Anthracite (1154.2) > Low- grade anthracite + Lignite (885.1) > Low-grade anthracite + Anthracite (842.7) > Low-grade anthracite (433.8)
.
31.5%, 33.1%, 30.6% . (m2 g-1) Commercial AC (1314.2) > Lignite (827.5) > Anthracite (758.8) > Anthracite + Lignite (598.6) > Low-grade anthracite + Anthracite (453.3) > Low-grade anthracite + Lignite (453.3) > Low-grade anthracite (367.4) 1.5 ~ 3.5
, (m2 g-1) Anthracite + Lignite (592.2) > Lignite (593.3) > Low-grade anthracite + Lignite (447.4) > Anthracite (395.4) > Low-grade anthracite + Anthracite (389.4) > Commercial AC (208.1) > Low-grade anthracite (66.5)
1.8 ~ 2.9 . , (cm3 g-1) Lignite (0.753)
> Commercial AC (0.692) > Anthracite + Lignite (0.654) > Anthracite (0.608) > Low-grade anthracite + Lignite (0.593) > Low-grade anthracite + Anthracite (0.523) > Low-grade anthracite (0.242)
. (cm3 g-1)
, (cm3/g) Lignite (0.392) > Low-grade anthracite + Lignite (0.388) > Anthracite + Lignite (0.383) > Low-grade anthracite + Anthracite (0.314) > Anthracite
374
Figure 7. Fourier-transform infrared spectra of (a) powdered activated carbons, and (b) pelletized activated carbons.
Table 4. Physical property of pelletized activated carbons
Physical property
Density (g mL-1)
Low-grade Anthracite 1.5 99.2 98.2 0.55 Low-grade Anthracite + Anthracite 1.8 99.5 97.9 0.40
Low-grade Anthracite + Lignite 1.6 99.2 97.9 0.39
Anthracite 1.7 99.6 97.7 0.38 Anthracite + Lignite 1.6 99.1 97.5 0.36 Lignite 1.4 99.4 97.0 0.33 Commercial AC 2.0 95.8 97.1 0.41
Standard (KSM 1802) under 10
above 90
above 90
under 0.56
(0.282) > Commercial AC (0.142) > Low-grade anthracite (0.084) 34.1% ,
2.0 ~ 2.8 . () , Low-grade anthracite + Lignite
(26.7) > Low-grade anthracite + Anthracite (24.8) > Low-grade anthracite (22.3) > Anthracite + Lignite (21.9) > Lignite (21.2) > Anthracite (21.0) > Commercial AC (18.2)
1.8% , 20
,
.
,
.
. ,
, 1.4 ~ 1.8%
,
. 99%
.
,
,
.
,
,
.
Figure 7 (a) , (b) FTIR
. Figure 7(a) , O-H (3,700 ~ 3,800 cm-1), C=O (1,550 cm-1), C-H (1,430 cm-1), C-O (978 cm-1) [29],
.
,
,
. Figure 7(b) , CMC
O-H (3,000 ~ 3,500 cm-1), -COOH (1,600 cm-1), C-H (1,430 cm-1), -CH2 (1,320 cm-1), C-O (1,000 cm-1)
[29],
. 15%
.
,
,
.
375
Figure 8. Breakthrough curve of activated carbon for (a) single benzene, (b) single xylene, and (c) combined benzene, toluene, and xylene.
3.5.
(a) , (b) , (c) ,
,
short term exposure limit (STEL) , . ,
. Figure 8(a) , (STEL 5 ppm)
(min) Lignite (320) > Anthracite (254)
Commercial AC (252) > Anthracite + Lignite (240) > Low- grade anthracite + Anthracite (207) > Low-grade anthracite + Lignite (207) > Low-grade Anthracite (100) ,
1.3 . Table 3
. , STEL 5 ppm ,
.
,
. Figure 8(b) , (STEL 150 ppm)
Lignite (160) > Anthracite + Lignite (133) > Anthracite (120) > Low-grade anthracite + Lignite (79) > Commercial AC (70) > Low-grade anthracite + Anthracite (60) > Low-grade Anthracite (22) ,
1.1 ~ 2.3 .
Table 3
, ( >
> ),
. Figure 8(c) , , ,
(STEL 305 ppm) (min) Lignite (115) > Anthracite + Lignite (70) > Commercial AC (67) > Anthracite (65) > Low-grade anthracite + Anthracite (56) > Low-grade anthracite + Lignite (55) > Low-grade Anthracite (31)
, ,
1.7
.
,
, , ,
.
4.
376
,
, . , (%) (43.0) >
(31.1) > (14.6)
,
(kcal kg-1) (7,086) > (5,162) >
(2,360) 30.2 ~ 68.1%
.
, 3.3 ~ 3.9, 1.1 ~ 3.8 .
,
,
. , 10
M , 4 mL g-1, 12 h,
25 24 h,
4, 900 , 4 h, 1 L min-1,
0.5 M --, 4 mL g-1, 2 h,
CMC 15% .
4,290 kcal kg-1 , 35%
, 1,154 ~ 1,420 m2 g-1
. ( 1,000 m2 g-1) 15 ~ 42% .
, BET
0.8 ~ 0.9 , 0.6 ,
1.9 ~ 2.8 ,
. FTIR ,
,
.
.
,
1.0 ~ 1.3, 1.1 ~ 2.3, 1.0 ~ 1.7 , (87.5%) > (11.2%) > (-9.3%) . , ,
5,640 kcal kg-1 , > >
.
.
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doi: 10.7464/ksct.2017.23.4.364 pISSN 1598-9712 eISSN 2288-0690 This is an Open-Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License (http://creativecommons.org/licences/ by-nc/3.0) which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.
1, 2, 3, 3, 3,* 1
46241 63 2 2
46241 63 2 3
51518 51-88
(2017 10 25 ; 2017 11 5 ; 2017 11 5 )
Characteristics on Chemical Activation and VOCs Adsorption of Activated Carbon according to Mixing Ratio of Anthracite and Lignite
Joon-Hyung Cho1, Sung-Kyu Kang2, Min-Kyoung Kang3, Kuk Cho3, and Kwang-Joong Oh3,* 1Division of Creative Low Impact Development and Management for Ocean Port City Infrastructures, Pusan National University
2, Busandaehak-ro 63beon-gil, Geumjeong-gu, Busan, 46241, Republic of Korea 2Department of Civil and Environmental Engineering, Pusan National University
2, Busandaehak-ro 63beon-gil, Geumjeong-gu, Busan, 46241, Republic of Korea 3Department of Environmental Chemistry, Korea Polytachnic VII Collage
51-88, Oedongballim-ro, Seongsan-gu, Changwon-si, Gyeongsangnam-do, 51518, Republic of Korea
(Received for review October 25, 2017; Revision received November 5, 2017; Accepted November 5, 2017)
·
, , ,
. , ,
. · , , , ,
1,154 ~ 1,420 m2 g-1 ,
, . , ,
5,640 kcal kg-1 , > >
.
: , , , ,
Abstract : In this study, to improve the low surface area of domestic anthracite as raw materials of activated carbon, characteristics on chemical activation and VOCs adsorption of activated carbon according to mixing ratio of anthracite and lignite. For these, properties of raw materials, parameter characteristics of preparation processes for activated carbon, and VOCs adsorption characteristic of the prepared activated carbon are analyzed. The experimental results showed that, the domestic anthracite had disadvantages of high contents for ash and lead, arsenic, which were exceeded for the heavy metal limits, in the properties of raw materials. To improve these diadvantages, using the mixing ratio of anthracite and lignite, and the optimum conditions for pretreatment, activation, washing, and pellitization process, the activated carbon had a range of BET (Brunauer-Emmett-Teller) surface area of 1,154 ~ 1,420 m2 g-1 with mesopore development and hydrophobic surface property. The carbons were satisfied
364
365
with the quality standard for granular activated carbon, and had similar physicochemical properties with the commercial activated carbon. The minimum mixing condition for commercial VOCs activated carbon performance must have the caloric value of above 5,640 kcal kg-1, and the carbon had higher adsorption capacity with order of xylene > toluene > benzene according to more higher molcular weight and hydrophobic property.
Keywords : Activated carbon, Chemical activation, Anthracite, Lignite, Volatile organic compounds
1.
,
. , , ,
,
[1]. 2015
, , ,
[2],
,
,
. ,
50 ,
10 1,000
· ,
19 ~ 36% [1]. ( , , ) 50,767
99.6%
, , ,
79.8%
[3].
, , , , , ,
4, 5,000
[4]. 3 M, DuPont
,
Calgon, Norit
[5].
, 15 [6], , ,
, 20 .
, 24,300/
38%
, 2014 115,429 2006 13%
[7].
. ,
, , ,
,
.
2 . ,
, 936 2,381
94,600 ~ 197,490
[8,9].
(62 ~ 70%) (33~35%)
.
.
2 ,
,
. ,
, (phosphoric acid), (zinc chloride), (potassium carbonate), (sodium hydroxide), (potassium hydro- xide) [12-14].
, ,
, , ,
[10-12].
,
, Kong et al. [13]
, 920 m2 g-1 . Kim,
366
Figure 1. Schematic diagram of activation process reactor.
et al. [14] 2 , 900 ~ 1,000 m2 g-1 .
1,000 m2 g-1
.
, Yoon et al. [15]
1,014 ~ 1,093 m2 g-1
, Kim et al. [16]
1,039 ~ 1,232 m2 g-1
, Choi et al. [17] ·
1,084 m2 g-1 .
,
,
.
, , ,
, , ,
,
BET (Brunauer–Emmett–Teller) ,
, FTIR (Fourier Transform Infrared) .
.
2.
2.1.
, .
8 ~ 35 mesh .
(Nitric acid, Samchun, KOR, purity 60%), (Hydro- chloric acid, Samchun, KOR, purity 35 ~ 37%), (Phophoric acid, Samchun, KOR, purity 85%), (Sulfuric acid, Junsei, JPN, purity 95%) ,
(Potassium hydroxide, Samchun, KOR, purity 85%) . CMC (Car- boxylmethyl cellulose sodium salt, Samchun, KOR), PVA (Polyvinyl alcohol, Samchun, KOR), (Starch, Samchun, KOR), (Gum arabic, Samchun, KOR) .
2.2.
, , , , , .
(OV-11/CTB-10, Jelo Tech, KOR) -0.1 MPa, 90 , 24 h
,
(SH-820F, Seyoung Scientific, KOR)
, (0.5 ~ 16 M)
(1 ~ 5 mL g-1), (6 ~ 48 h) .
367
Table 1. Proximate, element, caloric value, heavy metal analysis for low-grade anthracite, anthracite, and ligniet as raw material of activated carbon
Items Analyzed items Unit
Ash % 43.0 31.13 14.55 - Fixed carbon % 49.10 60.99 76.28 -
Element
C % 26.20 62.50 80.1 - H % 1.10 0.80 3.00 - O % 1.10 2.00 4.30 - N % 0.40 0.40 1.70 - S % 0.08 0.24 0.43 - Cl % 0.08 0.01 0.00 -
Caloric value
Lower heating value
Heavy metal
Hg mg kg-1 0.00 0.04 0.00 - Cd mg kg-1 0.00 0.61 1.62 1 Pb mg kg-1 39.90 33.90 9.00 10 As mg kg-1 2.20 7.60 0.00 2 Cr mg kg-1 33.20 57.80 47.3 - Co mg kg-1 5.50 8.20 12.9 - Cu mg kg-1 5.20 28.60 0.0 - Mn mg kg-1 24.50 74.50 693 - Ni mg kg-1 11.40 45.30 31.70 - Tl mg kg-1 0.00 0.00 0.00 - V mg kg-1 47.80 20.10 7.40 -
(25 ~ 90 ) (6 ~ 48 h) ,
115 . 24 h . Figure 1 (STF-15/
75/610, Carbolite Ltd., UK) , (Euro- therm 2408CP, Carbolite Ltd., UK) 1,500
, 16
,
. 1,000 mm, 500 mm , 6
. 1,000 mm, 50 mm, 5 mm,
, , 0.5 ~ 5.0 L min-1
.
20 ,
,
. , ,
30 g
,
99.9% (0.5 ~ 2 L min-1)
10 min-1 (700 ~ 900 )
, (2 ~ 5 h)
. ,
,
.
(0.1 ~ 5 M) (1 ~ 4 mL g-1), (0.5 ~ 4 h)
, pH
, ,
-0.1 MPa, 90 , 24 h .
, (5 ~ 15%)
-0.1 MPa, 90 , 24 h .
BET , , FTIR . BET
(Micromeritics ASAP 2020, USA)
90 , 10 min-1, 350 , 4 h
-196 ,
0.05 ~ 0.15 P/P0 5
0.9999 , C . KSM 1802 , , , , FTIT
(IRAffinity-1 Shimadzu, Japan) .
(ASTM D6646-03)
,
,
(50 ppm), (5,000 ppm),
, , (10,050 ppm)
,
(ppbRAE 3000, REA systems, Inc., USA)
. 3
.
368
Figure 2. BET surface area and ash content of activated carbon according to (a) pretreatment agents, (b) HNO3 concentration, (c) HNO3/ anthracite ratio, and (d) pretrement time in pretreatment process.
, , ,
,
. , (%) (8.9) > (6.1)
(6.1)
, (%)
(43.0) > (31.1) > (14.6)
11.9 ~ 28.4% , (%)
(76.3) > (61.0) > (49.1)
.
,
,
. , C (%) (80.1) > (62.5) >
(26.2)
, H (%) 3%
. O (%) 5%
, N, S, Cl 0.5%
. (kcal kg-1) , (7,086) > (5,162) > (2,360) .
7,400 kcal kg-1 30.2 ~ 68.1%
, C
. , (mg kg-1) (802.9) >
(276.7) > (169.7) , Pb
(mg kg-1) (39.9) > (33.9) > (9.0) 10 mg kg-1 , As (mg kg-1) (7.6) >
(2.2) > (0.0)
2 mg kg-1 , Cd (mg kg-1) (1.62) > (0.61) > (0.0)
1 mg kg-1 .
, Cd, Pb, As 3
.
3.2.
.
,
.
3.2.1.
Figure 2 (a) , (b)
369
Table 2. Coagulation properties of anion and cation in aqueous solution
Anion→ Cl- NO3 - SO4
Cation↓
Ag+ I S S I Hg+ I S VSS I Ba2+ S S I I Ca2+ S S VSS I Cu2+ S S S I Cd2+ S S S I Co2+ S S S I Fe2+ S S S I Hg2+ S S VSS I Mg2+ S S S I Mn2+ S S S I Ni2+ S S S I Pb2+ I S I I Sr2+ S S VSS I Zn2+ S S S I Al3+ S S S I As3+ S X X X Cr3+ S S S I Fe3+ S S S I V3+ S S S I
Note : S = soluble (>5000 mg L-1), SS = slightly soluble (2000-5000 mg L-1), VSS = very slightly soluble (20-2000 mg L-1), I = insoluble (< 20 mg L-1), X = not compound.
, (c) , (d)
25 24 h, ,
900 , 4 h, 1 L min-1, (KOH/ anthracite, wt% wt%-1) 4 , 0.5 M , , 4 mL g-1, 2 h
. Figure 2(a) , (m2
g-1) (1685.4) > (539.9) > (210.4) > (39.7) .
(SiO2) 49 ~ 57%, (Al2O3) 27 ~ 31%, (Fe2O3) 4 ~ 10%, (CaO) 2 ~ 6%, (MgO) 0.4 ~ 1.3%
[18]. Equation (1)~(13)
, ,
[19-23], Table 2
[24,25]
, , , . ,
, , ,
.
.
Al2O3(s) + 6HCl(aq) → 2AlCl3(aq) + 3H2O (5)
Fe2O3(s) + 6HCl(aq) → 2FeCl3(aq) + 3H2O (6)
CaO(s) + 2HCl(aq) → CaCl2(aq) + H2O (7)
Al2O3(s) + 3H2SO4(aq) → Al2[SO4]3(aq) + 3H2O (8)
Fe2O3(s) + 3H2SO4(aq) → Fe2[SO4]3(aq) + 3H2O (9)
CaO(s) + H2SO4(aq) → CaSO4(s) + H2O (10)
Al2O3(s) + H3PO4(aq) → 2Al[PO4](s) + 3H2O (11)
Fe2O3(s) + H3PO4(aq) → 2Fe[PO4](s) + 3H2O (12)
3CaO(s) + 2H3PO4(aq) → Ca3[PO4]2(s) + 3H2O (13)
(%) , (28.1) >
(26.8) > (22.5) > (21.6) 3
.
.
. Figure 2(b) ,
(m2 g-1) 16 M (1830.0) > 10 M (1829.9) > 5 M (1565.4) > 1 M (1194.5) > 0.1 M (1027.0)
, 10 M .
,
.
, 0.5 M (28.6) > 1 M (27.2) > 5 M (23.8) > 10 M (21.6) 16 M (21.6)
.
10 M .
370
Figure 3. BET surface area of activated carbon according to (a) mixing temperature, and (b) mixing time in mixing process.
Figure 2(c) , (m2 g-1) 5 mL g-1 (1832.1) > 4 mL g-1 (1829.9) > 3 mL g-1 (1687.3) > 2 mL g-1 (1431.8) > 1 mL g-1 (423.8)
, 4 mL g-1
.
,
. (%) , 1 mL g-1 (31.55) > 2 mL g-1 (25.0) > 3 mL g-1 (22.5) > 4 mL g-1 (21.6) 5 mL g-1 (21.6) .
4 mL g-1 . Figure 2(d) , (m2
g-1) 48 h (1708.7) 24 h (1685.4) 12 h (1685.4) > 6 h (1156.5) 6 h 12 h . 12 h ,
.
(%) 6 h (30.8) > 12 h (21.6) 24 h (21.5) 48 h (21.3) .
12 h .
3.2.2.
Figure 3 (a) , (b)
10 M , 4 mL g-1, 12 h,
, 900 , 4 h, 1 L min-1, (KOH/anthracite, wt% wt%-1) 4
, 0.5 M , , 4 mL g-1, 2 h .
Figure 3(a) , (m2 g-1) 90 (1685.4) > 55 (1675.2) > 25 (1662.8)
.
,
1.4%
.
25 . Figure 3(b) , (m2 g-1)
48 h (1686.2) > 24 h (1685.4) > 12 h (1495.4) > 6 h (1256.5) , 24 h .
24 h
, 24 h .
3.2.3.
Figure 4 (a) , (b) , (c) , (d)
Figure 4(d)
.
10 M , 4 mL g-1, 12 h, 25 24 h,
0.5 M , , 4 mL g-1, 2 h
. Figure 4(a) , (KOH/anthracite,
wt% wt%-1) (m2 g-1) 4 (1829.9) > 5 (1435.5) > 3 (1329.3) > 2 (791.1)
4
,
. Equation (14) C KOH
1 : 3 [11,26,27],
1 : 4
,
.
4
.
371
Figure 4. BET surface area of activated carbon according to (a) KOH/anthracite ratio, (b) activation temperature and time, (c) nitrone flow rate, and (d) caloric value in activation process [note : the analysis results for ash and carbon content were included in Figure 4(d)].
6KOH + 2C → 2K + 3H2 + 2K2CO3 (14)
Figure 4(b) , 4 h (m2 g-1) 900 (1829.9) > 800 (1740.5) > 700 (1500.5)
, 900 . Equation (14)
Equation (15) ~ (18) 800
[27],
. 900
(m2 g-1) 4 h (1829.9) > 3 h (1685.4) > 5 h (1450.5) > 2 h (1136.4) > 1 h (1025.4)
4 h ,
. 4 h
.
900 , 4 h .
K2CO3 → K2O + CO2 (at 700 ~ 800 ) (15)
CO2 + C → 2CO (16)
Figure 4(c) ,
(m2 g-1) 2.0 L min-1 (1875.9) 1.5 L min-1 (1864.5)
1.0 L min-1 (1829.9) > 0.5 L min-1 (1155.4) 0.5 L min-1
1.0 L min-1
.
, , .
1.0 L min-1 . Figure 4(d) ,
(m2 g-1) 7,086 kcal kg-1 (2073.1) > 6,124 kcal kg-1 (1915.0) > 5,162 kcal kg-1 (1,685.4) > 3,761 kcal kg-1
(1,230.6) > 2,360 kcal kg-1 (633.5)
, . 1,000 m2 g-1
3,300 kcal kg-1 , 39% .
3.2.4.
Figure 5 (a) , (b) , (c) , (d)
372
Figure 5. BET surface area of activated carbon according to (a) washing agents, (b) HCl concentration, (c) HCl/anthracite ratio, and (d) washing time in washing process.
Figure 6. BET surface area and hardness of activated carbon according to (a) binder kinds, and (b) binder content in pelletization process.
HW (hot water), CW (cold water) . 10 M ,
4 mL g-1, 12 h,
25 24 h, ,
900 , 4 h, 1 L min-1, (KOH/anthracite, wt% wt%-1) 4 .
Figure 5(a) , (m2 g-1) HCl-HW-CW (1829.9) HW-CW (425.3) > CW (280.8)
1,400 m2 g-1
. Equation (14) ~ (18)
, ,
,
. ,
85
.
--
.
Figure 6 (a) , (b)
373
Table 3. BET surface area, pore volume, and average pore width of pelletized activated carbons
Sample Low-grade anthracite
Low-grade anthracite + Anthracite
activated carbon
BET surface area (m2 g-1) 433.8 842.7 885.1 1154.2 1191.9 1419.7 1522.3
Micropore area (m2 g-1) 367.4 453.3 437.7 758.8 598.6 827.5 1314.2
External area (m2 g-1) 66.5 389.4 447.4 395.4 593.3 592.2 208.1
Total pore volume (cm3 g-1) 0.242 0.523 0.593 0.608 0.654 0.753 0.692
Micropore volume (cm3 g-1) 0.158 0.208 0.205 0.326 0.271 0.361 0.55
Mesopore volume (cm3 g-1) 0.084 0.314 0.388 0.282 0.383 0.392 0.142
Average pore width () 22.3 24.8 26.7 21.0 21.9 21.2 18.2
10 M , 4 mL g-1, 12 h, 25 24 h,
, 900 , 4 h, 1 L min-1, (KOH/anthracite, wt% wt%-1) 4,
0.5 M , , 4 mL g-1, 2 h
. Figure 6(a) ,
(m2 g-1) CMC (1250.4) > Starch (1173.6) > Guargum (1120.9) > PVA (1040.7) . Lozano-Castello et al. [28] CMC
, PVA
.
. (%) , CMC (94) > PVA (67) > Guargum (51) > Starch (36)
, KSM 1802 90%
-25.8% , CMC
.
CMC , CMC
. Figure 6(b) , (m2
g-1) 0% (1685.5) > 5% (1541.1) > 10% (1379.9) > 15% (1250.4)
. (%)
, 15% (94) > 10% (84) > 5% (77) 0% (10) 5% , 5% 15%
. KSM 1802
90%
15% .
3.4.
,
BET , , FTIR .
3.4.1. BET
BET
(m2 g-1) , Commercial AC (1522.3) > Lignite (1419.7) > Anthracite + Lignite (1191.9) > Anthracite (1154.2) > Low- grade anthracite + Lignite (885.1) > Low-grade anthracite + Anthracite (842.7) > Low-grade anthracite (433.8)
.
31.5%, 33.1%, 30.6% . (m2 g-1) Commercial AC (1314.2) > Lignite (827.5) > Anthracite (758.8) > Anthracite + Lignite (598.6) > Low-grade anthracite + Anthracite (453.3) > Low-grade anthracite + Lignite (453.3) > Low-grade anthracite (367.4) 1.5 ~ 3.5
, (m2 g-1) Anthracite + Lignite (592.2) > Lignite (593.3) > Low-grade anthracite + Lignite (447.4) > Anthracite (395.4) > Low-grade anthracite + Anthracite (389.4) > Commercial AC (208.1) > Low-grade anthracite (66.5)
1.8 ~ 2.9 . , (cm3 g-1) Lignite (0.753)
> Commercial AC (0.692) > Anthracite + Lignite (0.654) > Anthracite (0.608) > Low-grade anthracite + Lignite (0.593) > Low-grade anthracite + Anthracite (0.523) > Low-grade anthracite (0.242)
. (cm3 g-1)
, (cm3/g) Lignite (0.392) > Low-grade anthracite + Lignite (0.388) > Anthracite + Lignite (0.383) > Low-grade anthracite + Anthracite (0.314) > Anthracite
374
Figure 7. Fourier-transform infrared spectra of (a) powdered activated carbons, and (b) pelletized activated carbons.
Table 4. Physical property of pelletized activated carbons
Physical property
Density (g mL-1)
Low-grade Anthracite 1.5 99.2 98.2 0.55 Low-grade Anthracite + Anthracite 1.8 99.5 97.9 0.40
Low-grade Anthracite + Lignite 1.6 99.2 97.9 0.39
Anthracite 1.7 99.6 97.7 0.38 Anthracite + Lignite 1.6 99.1 97.5 0.36 Lignite 1.4 99.4 97.0 0.33 Commercial AC 2.0 95.8 97.1 0.41
Standard (KSM 1802) under 10
above 90
above 90
under 0.56
(0.282) > Commercial AC (0.142) > Low-grade anthracite (0.084) 34.1% ,
2.0 ~ 2.8 . () , Low-grade anthracite + Lignite
(26.7) > Low-grade anthracite + Anthracite (24.8) > Low-grade anthracite (22.3) > Anthracite + Lignite (21.9) > Lignite (21.2) > Anthracite (21.0) > Commercial AC (18.2)
1.8% , 20
,
.
,
.
. ,
, 1.4 ~ 1.8%
,
. 99%
.
,
,
.
,
,
.
Figure 7 (a) , (b) FTIR
. Figure 7(a) , O-H (3,700 ~ 3,800 cm-1), C=O (1,550 cm-1), C-H (1,430 cm-1), C-O (978 cm-1) [29],
.
,
,
. Figure 7(b) , CMC
O-H (3,000 ~ 3,500 cm-1), -COOH (1,600 cm-1), C-H (1,430 cm-1), -CH2 (1,320 cm-1), C-O (1,000 cm-1)
[29],
. 15%
.
,
,
.
375
Figure 8. Breakthrough curve of activated carbon for (a) single benzene, (b) single xylene, and (c) combined benzene, toluene, and xylene.
3.5.
(a) , (b) , (c) ,
,
short term exposure limit (STEL) , . ,
. Figure 8(a) , (STEL 5 ppm)
(min) Lignite (320) > Anthracite (254)
Commercial AC (252) > Anthracite + Lignite (240) > Low- grade anthracite + Anthracite (207) > Low-grade anthracite + Lignite (207) > Low-grade Anthracite (100) ,
1.3 . Table 3
. , STEL 5 ppm ,
.
,
. Figure 8(b) , (STEL 150 ppm)
Lignite (160) > Anthracite + Lignite (133) > Anthracite (120) > Low-grade anthracite + Lignite (79) > Commercial AC (70) > Low-grade anthracite + Anthracite (60) > Low-grade Anthracite (22) ,
1.1 ~ 2.3 .
Table 3
, ( >
> ),
. Figure 8(c) , , ,
(STEL 305 ppm) (min) Lignite (115) > Anthracite + Lignite (70) > Commercial AC (67) > Anthracite (65) > Low-grade anthracite + Anthracite (56) > Low-grade anthracite + Lignite (55) > Low-grade Anthracite (31)
, ,
1.7
.
,
, , ,
.
4.
376
,
, . , (%) (43.0) >
(31.1) > (14.6)
,
(kcal kg-1) (7,086) > (5,162) >
(2,360) 30.2 ~ 68.1%
.
, 3.3 ~ 3.9, 1.1 ~ 3.8 .
,
,
. , 10
M , 4 mL g-1, 12 h,
25 24 h,
4, 900 , 4 h, 1 L min-1,
0.5 M --, 4 mL g-1, 2 h,
CMC 15% .
4,290 kcal kg-1 , 35%
, 1,154 ~ 1,420 m2 g-1
. ( 1,000 m2 g-1) 15 ~ 42% .
, BET
0.8 ~ 0.9 , 0.6 ,
1.9 ~ 2.8 ,
. FTIR ,
,
.
.
,
1.0 ~ 1.3, 1.1 ~ 2.3, 1.0 ~ 1.7 , (87.5%) > (11.2%) > (-9.3%) . , ,
5,640 kcal kg-1 , > >
.
.
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De gemaakte PDF-documenten kunnen worden geopend met Acrobat en Adobe Reader 5.0 en hoger.) /NOR <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> /PTB <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> /SUO <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> /SVE <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> /ENU (Use these settings to create Adobe PDF documents for quality printing on desktop printers and proofers. Created PDF documents can be opened with Acrobat and Adobe Reader 5.0 and later.) >> /Namespace [ (Adobe) (Common) (1.0) ] /OtherNamespaces [ << /AsReaderSpreads false /CropImagesToFrames true /ErrorControl /WarnAndContinue /FlattenerIgnoreSpreadOverrides false /IncludeGuidesGrids false /IncludeNonPrinting false /IncludeSlug false /Namespace [ (Adobe) (InDesign) (4.0) ] /OmitPlacedBitmaps false /OmitPlacedEPS false /OmitPlacedPDF false /SimulateOverprint /Legacy >> << /AddBleedMarks false /AddColorBars false /AddCropMarks false /AddPageInfo false /AddRegMarks false /ConvertColors /NoConversion /DestinationProfileName () /DestinationProfileSelector /NA /Downsample16BitImages true /FlattenerPreset << /PresetSelector /MediumResolution >> /FormElements false /GenerateStructure true /IncludeBookmarks false /IncludeHyperlinks false /IncludeInteractive false /IncludeLayers false /IncludeProfiles true /MultimediaHandling /UseObjectSettings /Namespace [ (Adobe) (CreativeSuite) (2.0) ] /PDFXOutputIntentProfileSelector /NA /PreserveEditing true /UntaggedCMYKHandling /LeaveUntagged /UntaggedRGBHandling /LeaveUntagged /UseDocumentBleed false >> ] >> setdistillerparams << /HWResolution [2400 2400] /PageSize [612.000 792.000] >> setpagedevice
