- Email: [email protected]
INFLUENCE OF PETROGRAPHICAL FACTORS ON HYDROGENATION OF INERTINITE RICH COALS FROM THE UPPER SILESIAN COAL BASIN OF POLAND
INFLUENCE OF PETROGRAPHICAL FACTORS ON HYDROGENATION OF INERTINITE RICH COALS FROM THE UPPER SILESIAN COAL BASIN OF POLAND Wieslaw Gabzdyl and Atul Kumar Varma Institute of Applied Geology, Faculty of Mining, Silesian Technical University,ul.Katowicka2, 44-101 Gliwice, Poland INTRODUCTION Various workers found the fair correlation between the sum of preassumed reactive macérais (vitrinite and exinite) and hydrogénation of coals ~ . But this conventional method was found to be inadequate . Some researchers ' have ideas that low rank coals are more reactive during coal liquefaction. Rentel emphasized that coking properties of coals do not depend on inertinite content but on its associations with other macérais. Association of macérais (microlithotypes) may play important roles in coal liquefaction ' . Heng and Shibaoka found that inertinite macérais contributed significantly to the oil yield. EXPERIMENTAL With aim to find optimal associations of macérais (microlithotypes), six inertinite rich coal samples (I™11 > 30%) of different ranks as well as from different sedimentary faciès have been chosen from Upper Silesian Coal Basin of Poland. Two coal samples among them represent medium rank bitominous coking coals (A-l) (B-2) and the rest of four coal samples are low ranking non coking-coals (C-3, D-4, E-5 and F-6). The petrographical analysis (macérai and microlithotype compositions) and the mean reflectance of vitrinite in oil, Rm % were determined under the reflecting microscope and have been shown in Table-1. The technological parameters and sulphur content of coals were determined according to Polish standards and the results are placed in Table-1. TherFig. 1. Method of determination of AAmax under DTG mogravimetric analyses (DTG) of coals have been done and AAmax (main decomposition area during maximum rate of decomposition under DTG) was determined using planimeter according to the method proposed by researchers and shown in Fig.-l. These coal samples were crushed to <0. 1 mm and hydrogenated in the presence of earlier hydrogenated anthracene oil as a solvent without addition of any catalysts in 4-litre Hungarian autoclave. RESULTS AND DISCUSSION The degree of conversion, Sk (% mass) of organic substances of coal has been calculated according to the following formula and the results have been shown in Table-1.
719
M3 A 100
Mi - [M2 Sk =
x 100
Mi
Where, Sk = degree of conversion (% mass), Mi = mass of organic substances in the given coal sample, g M2 = mass of THF - ( tetrahydrofuran) insoluble costituents in the given coal sample, g M3 = mass of dry coal, g A = ash content (on dry basis) in the coal sample (% mass). The degree of conversion, Sk varies from 38.7 - 55.1% mass. Attention has been paid to the geological, petrographical, technological and DTG investigations. The effect of these factors on the degree of conversion, Sk, is very clearly reflected by the structure and the amount of microlithotypes, carbominerites and rocks. To show clear relations among these factors, calculation of index of hydrogénation is proposed, according to the following empirical formula mentioned below :
IH
Rt Rn
x C
R + (KM-KP)
D-4
60-
t r ^ S ^
50-
B-2
W-
C
G ^ ^
^
F-6 r = 0.85
Ε^*
^
30-
?n 2
4
6
8 10 IH Index of hydrogénation, IH
Fig.2. Correlation between degree of conversion, Sk and index of hydrogénation (IH).
0.9^
40
50
60
70
80
90
100
110 AAmax units (DTG)
Fig.3. Relation between AAmax units and Sk (% ma:
720
Where, IH = index of hydrogénation (proposed) Rt = reactive microlithotypes [W(60%) + K(75%) + WI(75%) + DK(90%) + TM(90°/o)] Rn = little reactive microlithotypes [In(60%) + KD(90%)] C = constant which varies with the rank of coal C = 1.00 and 0.75 for low rank coals (RS = 0.44 - 0.59%) and for medium rank coals (RS = 1. 12 1.21%) respectively. The calculated indices of hydrogénation are placed in the range varying from 2.5 - 8.9 . Proposed indices of hydrogénation, IH show good correlation coefficient (r = 0.85) with the degree of converl sion, Sk (Fig.-2).
Table-1. Petrographical, technological and DTG properties of coals, degree of conversion, Sk and index of hydrogénation, IH during coal liquefaction. Coal samples
Parameters |l. Macérai comp. mmf, %Vol. Vitrinite (Vt) Inertinite (I) Exinite (L) 2. Microlithotype (*) comp. % Vol. Vitrite (W) * 1 Inertite (In) * Clarite (K) * Durite (D) * Vitrinertite (WI) * Duroclarite (DK) * Clarodurite (KD) * Vitrinertoliptite (WL) * Other trimacerite (TM) * Carbominerite (KM) Carbopyrite (KP) Rocks (R) 3. Rank Rm % (mean reflectance) Volatile matter content
vdaf
F-6
E-5
D-4
C-3
B-2
A-l
56.6 32.9 10.5
62.2 30.5
56.6 37.8
54.2 37.5
54.5 45. 1
50.3 49.3
7.3
5.6
7.3
0.0
0.4
6.4
12.3
15.8
5.5
16.6 17.9
15.4
0.0 0.0
0.0 0.0
65.5
80.3
0.6 0.0 0.0 0.0 2.6 0.9 4.7
4.8
3.7
14.6
10.7
1.3 6.3
0.5 5.1
15.0
2.0
7.2 7.4 2.1
30. 1 19.7 10.5
33.1 11.5 22. 1 1. 1
18.5 34. 1
13.9 29.0
8.8
3.4 1.4 4.8
9.6 4.0 2.6
4.6 4.4 3.7 4.4 1.5
21.6
28.0
19.9
0.0 0.0 0.0 0.0 3.5 1.0 8.7
0.44
0.45
0.55
0.59
1. 12
1.21
45.9
39.5
42. 1
39.6
26.0
22.9
0.8
0.9
2.0 10.5
2. 1 13.7
4.1 1.8
4. Technological, % mass Wa
(moisture)
Ad
(ash)
9.8
10.0
16.9
11.8
10.2
14.6
5.6
2.7
St (total sulphur)
3.6
2.6
1.3
1.8
0.6
0.5
Sp (pyritic sulphur)
2. 1
1.5
0.7
1. 1
0.4
0.2
1.0
0.8
0.2
0.3
0.2
0. 1
85
50
108
80
64
92
44.6
38.7
55. 1
42.2
7.3
2.5
8.9
6.2
Sso4 (sulphatic sulphur) 5. DTG (thermogravimetric) AAmax units 6. Conversion Sk % mass
IH Explanations :
6. 1
6. 1
39. 1 48.4 7.4 | 5.6
*
= ace. to ICCP and without carbomierites (KM) and rocks (R), Rm = mean reflectance of vitrnite in oil
The coal sample E-5 is the exception, which at the obtained degree of conversion, Sk show quite difference in the amount of hydrogénation index (IH), which might be resulting from different macérai compositions in duroclarites and also may be due to the greater amount of pyrites in the coal sample. Very good correlation coefficient(r = 0.94) has been found between AAmax and Sk (Fig.-3).
721
CONCLUSIONS 1. Hydrogénation of the coals depend on the ranks of the coal. Coal liquefaction is difficult with the increase in the rank of coal. 2. The proposed index of hydrogénation, IH of coal appears to be directly proportional to the degree of conversion,Sk. 3. It seems that reactivity of duroclarite (DK), Vitrinertoliptite (WL) and trimacerite (TM) is greater than clarite and vitrinertite which is greater than vitrite during coal liquefaction . 4. It further appears that inertite (In) and clarodurite (KD) blocks or inhibits coal liquefaction. 5. The volatile matter content, V help in coal liquefaction. 6. Rocks (R) and carbominerites (KM) except pyrites and carbopyrites appear to be infavourable for coal liquefaction. 7. AAmax (decomposition area during maximum rate of decomposition under DTG) shows very good correlation with the degree of conversion, Sk. AAmax seams to depend on microlithotypic composition and rank of coals. 8. The effect of sedimentary facial conditions is not visible and needs to be interpreted after the study of hydrogénation residues. REFERENCES 1. Given,P.H., Cronauer,D.C., Spackman,W., Lovell,H.L., Davis,A. and Biswas, B. Fuel 1975, 54, 40 2. Inhatowicz,M., Kulczyka.J. and Potyka,W. Ogolnokrajowa konferencja na temat: Problemy badan wegla w pracach geologiczno-zlozowych w aspekcie nowych technologii jego utylizacji, Jaworze, 1984, 120-130 3. Miller,R.L., Baldwin,R.M., Fuel 1985, 64, 1235-1241 4. Steiler,M., Kaikreuth,W. and Hodek.W. Erdöl und kohle Erdgas-Petrochemie vereingt mit Brennstoff-chemie, 1987, Bd 40, Heft 9, 383-393 5. Gray,D., Barrass.G., Jezko.J. and Kershaw,J. R. Fuel 1980, 54,146 6. Given, P. H., Cronauer,D.C., Spackman,W. , Lovell,H.L. , Davis, A. and Biswas,B. Fuel 1975, 54, 34 7. Van Krevlen.D.W., Int. coal conversion conf. in Snyman.P.C., Int. J. Coal Geol. 1984, 14, 83 8. Rentel.K. Int.
J. Coal Geol.
(unpub.) cited
1987, 9, 77
9. Gabzdyl,W., Hanak,B. and Winnicki.J., Przeglad 10. Steiler,M., Int.
1982
J. Coal Geol.
Gorniczy
1984, 40, 26
1987, 9, 109
11. Heng.S., Shibaoka,M., Fuel 1983, 62, 610 12. Gabzdyl.W., Hanak.B. and Pietraszek,D. Koks Smola Gaz 1984, 29, 27
722
719
M3 A 100
Mi - [M2 Sk =
x 100
Mi
Where, Sk = degree of conversion (% mass), Mi = mass of organic substances in the given coal sample, g M2 = mass of THF - ( tetrahydrofuran) insoluble costituents in the given coal sample, g M3 = mass of dry coal, g A = ash content (on dry basis) in the coal sample (% mass). The degree of conversion, Sk varies from 38.7 - 55.1% mass. Attention has been paid to the geological, petrographical, technological and DTG investigations. The effect of these factors on the degree of conversion, Sk, is very clearly reflected by the structure and the amount of microlithotypes, carbominerites and rocks. To show clear relations among these factors, calculation of index of hydrogénation is proposed, according to the following empirical formula mentioned below :
IH
Rt Rn
x C
R + (KM-KP)
D-4
60-
t r ^ S ^
50-
B-2
W-
C
G ^ ^
^
F-6 r = 0.85
Ε^*
^
30-
?n 2
4
6
8 10 IH Index of hydrogénation, IH
Fig.2. Correlation between degree of conversion, Sk and index of hydrogénation (IH).
0.9^
40
50
60
70
80
90
100
110 AAmax units (DTG)
Fig.3. Relation between AAmax units and Sk (% ma:
720
Where, IH = index of hydrogénation (proposed) Rt = reactive microlithotypes [W(60%) + K(75%) + WI(75%) + DK(90%) + TM(90°/o)] Rn = little reactive microlithotypes [In(60%) + KD(90%)] C = constant which varies with the rank of coal C = 1.00 and 0.75 for low rank coals (RS = 0.44 - 0.59%) and for medium rank coals (RS = 1. 12 1.21%) respectively. The calculated indices of hydrogénation are placed in the range varying from 2.5 - 8.9 . Proposed indices of hydrogénation, IH show good correlation coefficient (r = 0.85) with the degree of converl sion, Sk (Fig.-2).
Table-1. Petrographical, technological and DTG properties of coals, degree of conversion, Sk and index of hydrogénation, IH during coal liquefaction. Coal samples
Parameters |l. Macérai comp. mmf, %Vol. Vitrinite (Vt) Inertinite (I) Exinite (L) 2. Microlithotype (*) comp. % Vol. Vitrite (W) * 1 Inertite (In) * Clarite (K) * Durite (D) * Vitrinertite (WI) * Duroclarite (DK) * Clarodurite (KD) * Vitrinertoliptite (WL) * Other trimacerite (TM) * Carbominerite (KM) Carbopyrite (KP) Rocks (R) 3. Rank Rm % (mean reflectance) Volatile matter content
vdaf
F-6
E-5
D-4
C-3
B-2
A-l
56.6 32.9 10.5
62.2 30.5
56.6 37.8
54.2 37.5
54.5 45. 1
50.3 49.3
7.3
5.6
7.3
0.0
0.4
6.4
12.3
15.8
5.5
16.6 17.9
15.4
0.0 0.0
0.0 0.0
65.5
80.3
0.6 0.0 0.0 0.0 2.6 0.9 4.7
4.8
3.7
14.6
10.7
1.3 6.3
0.5 5.1
15.0
2.0
7.2 7.4 2.1
30. 1 19.7 10.5
33.1 11.5 22. 1 1. 1
18.5 34. 1
13.9 29.0
8.8
3.4 1.4 4.8
9.6 4.0 2.6
4.6 4.4 3.7 4.4 1.5
21.6
28.0
19.9
0.0 0.0 0.0 0.0 3.5 1.0 8.7
0.44
0.45
0.55
0.59
1. 12
1.21
45.9
39.5
42. 1
39.6
26.0
22.9
0.8
0.9
2.0 10.5
2. 1 13.7
4.1 1.8
4. Technological, % mass Wa
(moisture)
Ad
(ash)
9.8
10.0
16.9
11.8
10.2
14.6
5.6
2.7
St (total sulphur)
3.6
2.6
1.3
1.8
0.6
0.5
Sp (pyritic sulphur)
2. 1
1.5
0.7
1. 1
0.4
0.2
1.0
0.8
0.2
0.3
0.2
0. 1
85
50
108
80
64
92
44.6
38.7
55. 1
42.2
7.3
2.5
8.9
6.2
Sso4 (sulphatic sulphur) 5. DTG (thermogravimetric) AAmax units 6. Conversion Sk % mass
IH Explanations :
6. 1
6. 1
39. 1 48.4 7.4 | 5.6
*
= ace. to ICCP and without carbomierites (KM) and rocks (R), Rm = mean reflectance of vitrnite in oil
The coal sample E-5 is the exception, which at the obtained degree of conversion, Sk show quite difference in the amount of hydrogénation index (IH), which might be resulting from different macérai compositions in duroclarites and also may be due to the greater amount of pyrites in the coal sample. Very good correlation coefficient(r = 0.94) has been found between AAmax and Sk (Fig.-3).
721
CONCLUSIONS 1. Hydrogénation of the coals depend on the ranks of the coal. Coal liquefaction is difficult with the increase in the rank of coal. 2. The proposed index of hydrogénation, IH of coal appears to be directly proportional to the degree of conversion,Sk. 3. It seems that reactivity of duroclarite (DK), Vitrinertoliptite (WL) and trimacerite (TM) is greater than clarite and vitrinertite which is greater than vitrite during coal liquefaction . 4. It further appears that inertite (In) and clarodurite (KD) blocks or inhibits coal liquefaction. 5. The volatile matter content, V help in coal liquefaction. 6. Rocks (R) and carbominerites (KM) except pyrites and carbopyrites appear to be infavourable for coal liquefaction. 7. AAmax (decomposition area during maximum rate of decomposition under DTG) shows very good correlation with the degree of conversion, Sk. AAmax seams to depend on microlithotypic composition and rank of coals. 8. The effect of sedimentary facial conditions is not visible and needs to be interpreted after the study of hydrogénation residues. REFERENCES 1. Given,P.H., Cronauer,D.C., Spackman,W., Lovell,H.L., Davis,A. and Biswas, B. Fuel 1975, 54, 40 2. Inhatowicz,M., Kulczyka.J. and Potyka,W. Ogolnokrajowa konferencja na temat: Problemy badan wegla w pracach geologiczno-zlozowych w aspekcie nowych technologii jego utylizacji, Jaworze, 1984, 120-130 3. Miller,R.L., Baldwin,R.M., Fuel 1985, 64, 1235-1241 4. Steiler,M., Kaikreuth,W. and Hodek.W. Erdöl und kohle Erdgas-Petrochemie vereingt mit Brennstoff-chemie, 1987, Bd 40, Heft 9, 383-393 5. Gray,D., Barrass.G., Jezko.J. and Kershaw,J. R. Fuel 1980, 54,146 6. Given, P. H., Cronauer,D.C., Spackman,W. , Lovell,H.L. , Davis, A. and Biswas,B. Fuel 1975, 54, 34 7. Van Krevlen.D.W., Int. coal conversion conf. in Snyman.P.C., Int. J. Coal Geol. 1984, 14, 83 8. Rentel.K. Int.
J. Coal Geol.
(unpub.) cited
1987, 9, 77
9. Gabzdyl,W., Hanak,B. and Winnicki.J., Przeglad 10. Steiler,M., Int.
1982
J. Coal Geol.
Gorniczy
1984, 40, 26
1987, 9, 109
11. Heng.S., Shibaoka,M., Fuel 1983, 62, 610 12. Gabzdyl.W., Hanak.B. and Pietraszek,D. Koks Smola Gaz 1984, 29, 27
722