liquefaction pathways of bituminous subbituminous coals andtheir

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always for the re-moisturized coals. The total evolution of CO, and CO from pyrolysis is changed significantly by cation- exchange. However, only in the case of CO does the evolution profile change significantly. After careful demineralization, a calcium form Zap or Wyodak coal can be prepared at pH= 8, which is similar to the raw coal with regard to pyrolysis and liquefaction behavior. At pH =8, cations are most likely to be coordinating multiple oxygen functionalities around themselves through electrostatic type interactions, which diminishes the importance of valency. Some of the moisture in a coal is associated with the cations. The moisture content has a larger role in liquefaction than in pyrolysis because it is present for a longer period of time. ACKNOWLEDGEMENTS This work was supported by the U.S. D.O.E. Pittsburgh Energy Technology Center under Contract No. DE-AC22-91 PC91026. REFERENCES 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. Whitehurst, D.b., Mitchell, T.O., and Farcasiu, M., Coal Liauefaction. The Chemistrv and Technoloav of Thermal Processes, Academic Press, NY (1 980). Mochida, I., Shimohara, T., Korai, Y., Fujitsu, H.. and Takeshita, IC, Fuel 62,659, (1983). Tyler, R.J. and Schafer, H.N.S., Fuel, 59, 487, (1980). Morgan, M.E. and Jenkins, Fuel, 65, 757, (1986). Morgan, M.E. and Jenkins, Fuel, 65, 764, (1986). Morgan, M.E. and Jenkins, Fuel, 65, 769, (1986). Wornat, M.J., and Nelson P.F., Energy and Fuel, 6 (2) (1992). Bishop, M., and Ward, D.L., Fuel, 37, 191, (1958). Vorres, KS., Energy and Fuel, 4 (5). 420 (1990). Schafer, H., Fuel, 49, 197, (1970). Serio, M.A., Kroo, E., Teng, H., Charpenay, S., and Solomon, P.R., 'The Dual Role of Oxygen Functions in Coal Pretreatment and Liquefaction: Crosslinking and Cleavage Reactions," Fifth Quarterly Report, U.S. DOE Contract No. DE-AC22-91-PC91026 (1992). van Bodegom, E., van Veen, J.A., van Kessel. G.M.M., Sinnige-Nijssen, M.W.A., and Stuiver, H.C.M, Fuel, 63, 346 (1984). Suuberg, EM., Lee, D., and Larsen, J.W., Fuel, 64, 1668, (1985). Suuberg, E.M., Unger, P.E., and Larsen, J.W., Energy & Fuels, 1, 305, (1987). Solomon, P.R., Serio, M.A., Deshpande, G.V., and Kroo, E., Energy & Fuels, 4 (I), 42, (1 990). Schafer, H., Fuel, 51, 4, (1972). 582
Table 1. F'yrolysis Results of Vacuum Dried Modified Zap Samples. Coal Pyndysb Products (d.% ,d& Tars Cop CO Ha0 CH4 Char Fresh 7 8.9 14.7 14.3 2.2 57 Demin. 20 4.8 10.4 8.4 2.7 fA Demin. +IC+ (pH6) 11 8.6 9.9 16.0 1.9 57 Demin. + Ce* (pH8) 10 8.6 13.5 10.3 2.4 58 Demin. + Be* (pH8) 6 11.7 15.8 18.6 2.6 55 Demin. + K+ (pHl2.5) 5 9.9 12.4 13.5 1.6 57 Demin. + Ce* (pHl2.5) 4 8.2 22.6 12.6 2.0 51 Demin. + Ba* (pHl2.5) 3 10.5 24.1 15.5 2.6 52 Table 2. Liquefaction Results ofvacuum Dried Modified Zap Samples. Toluene Solubles GlM Total Oils Auphaltenes Cop CO CH4 Fresh 26 12 14 4.3 0.24 0.25 Demin. 52 26 26 1.1 0.43 0.27 Demin. +I(+ (pH8) 30 11 19 7.7 0.27 0.17 Demin. + Ca++ (pH81 25 13 12 2.7 0.30 0.22 Demin. + Ba++ (pH81 37 25 12 7.3 0.40 0.20 Demin. + IC+ (pH1z.5) Demin. + Ca++ (pHl2.5) 17 * 5 * 12 3 5.0 0.7 0.24 0.04 0.27 0.08 Demin. + Ba++ (pHl2.5) 15 15 0.5 0.3 0.27 0.02 Yields Calculated by Difierenca were Negative. Solvent heorparation is Sunperred. Notes V3.R = Vohmetrlc Swelling Ratio in Pyridine, Pa = pyridine Sohbles (daO Moisture was Dstermined by TG-FlYR and ls Reponed on an Abreesived Baals. NM =Not Measured. Table 4. The Carbonyl and Phenolic Contents of Zap and Wyodak Coals Determined by Barium Titration. (meq g' daf basis) Carboxyl Groups Phenolic Groups Total Acidity Zap Lignite 2.52 6.74 9.26 Wyodak Sub. 2.40 5.76 8.16 583
Page 1 and 2:
LIQUEFACTION PATHWAYS OF BITUMINOUS
Page 3 and 4:
the conversion of A+P and O+G with
Page 5 and 6:
Asphaltcncs PrCasphaltenCS Cwr%, da
Page 7 and 8:
NEW DIRECTIONS TO PRECONVERSION PRO
Page 9 and 10:
ecause of incorporation of the coal
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should be considered more. The step
Page 13 and 14:
17 18 Run no. 0 cys I ToS-CyS TS-To
Page 15 and 16:
INTRODUCTION Effects of Thermal and
Page 17 and 18:
apid decline in modulus. The loss m
Page 19 and 20:
-0.01- . 04 5 -0.03- E 6 -0.0s- c)
Page 21 and 22:
Assessment of Small Particle Iron O
Page 23 and 24:
yields are calculated by subtractin
Page 25 and 26:
conversion is greater than the corr
Page 27 and 28:
Table 3. Effect of Superfine Iron O
Page 29 and 30:
EFFECT OF A CATALYST ON THE DISSOLU
Page 31 and 32:
inherent volatility of Mo(CO), perm
Page 33 and 34:
Analysis of the quantity and compos
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$ EO .- 0 m L 0 c 0 0 > 40 300 350
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0 0 0 0 0.000 0.005 0.010 0.015 0.0
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of these studies indicate that cont
Page 41 and 42:
Different levels of adsorption occu
Page 43 and 44:
Nominal 2 Table 1. Concentration of
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- iF m 1.6 1.4 1.2 - - - 1- 0 0.8 -
Page 47 and 48:
RESULTS AND DISCUSSION Swelling of
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. . % . . 9 'HF 0 0 0 *. . 0 . . 0
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1.50 KQ 1.00 0.50 I / ' 02 525 I 1
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hydrogen atoms. The hydrogen atoms
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D to generate more D atoms. It is r
Page 57 and 58: 12. a. Poutsma, M. L.; Dyer, C. W.
Page 59 and 60: Figure 3. Minimum Steps to Explin D
Page 61 and 62: Apoaratus and Procedure Microflow R
Page 63 and 64: Model ComDound Test Figure 5 shows
Page 65 and 66: Figure 1. High resolution gas chrom
Page 67 and 68: Figure 5. Product distribution for
Page 69 and 70: THQ at somewhat higher temperatures
Page 71 and 72: areas of the particles and the SEM
Page 73 and 74: Experimental Catalyst Precursors an
Page 75 and 76: impregnating solvent. Table 3 shows
Page 77 and 78: of MoCo-TC2 at the level of 0.5 wt%
Page 79 and 80: Table 4. Effect of Temperature Prog
Page 81 and 82: In the past, chemical treatments in
Page 83 and 84: The effect of Corn20 preaatment on
Page 85 and 86: Reaction Time Figure 1 - Schematic
Page 87 and 88: DISSOLUTION OF THE ARGONNE PREMIUM
Page 89 and 90: A much more def~tive trend is seen
Page 91 and 92: EFFECT OF CHLOROBENZENE TREATMENT O
Page 93 and 94: same conditions and an extraction t
Page 95 and 96: ACKNOWLEDGEMENT The authors thank t
Page 97 and 98: THE STRUCTURAL &=RATION OF HUMINlTE
Page 99 and 100: to be originally derived from demet
Page 101 and 102: 145 30 I --/---Jh I , , I I , 250 2
Page 103 and 104: THE EFFECTS OF MOISTURE AND CATIONS
Page 105 and 106: 1 for the Zap lignite. These result
Page 107: content of the samples ion-exchange
Page 111 and 112: 585 I
Page 113 and 114: EFFECT OF TEMPERATURE, SAMPLE SI2E
Page 115 and 116: of some of the thermobalance runs.
Page 117 and 118: 2. The mechanism of drying is a uni
Page 119 and 120: Influence of Drying and Oxidation 0
Page 121 and 122: "c gives W conversion mpared to the
Page 123 and 124: Table 1. Products dismbutions (dmmf
Page 125 and 126: - 50 45 40 E 35 2 30 E T) 25 ap 20
Page 127 and 128: Influence of Drying and Oxidation o
Page 129 and 130: FTIR . . of the L m To investigate
Page 131 and 132: CONCLUSIONS The characexizntion of
Page 133 and 134: A b S 0 r b a n C e A b s 0 r b a n
Page 135 and 136: An NMR Investigation of the Effd of
Page 137 and 138: for determining the area of the pea
Page 139 and 140: of the ronl roniponcnte nnd (2) the
Page 141 and 142: 2w 180 160 9 140 120 P loo f 80 P O
Page 143 and 144: 25 I 20 ' + 0 Drying lime, hours Fi
Page 145 and 146: substructure have been identified a
Page 147 and 148: Pyridine extraction showed that 60
Page 149 and 150: Figure 1. Reflected white-light pho
Page 151 and 152: Table 3. Pyridine Extraction Sample
Page 153 and 154: A bang-bang control strategy was us
Page 155 and 156: increased from 120°C to 135”C, r
Page 157 and 158: * wt% based on the amount of naphth
Page 159 and 160:
Use of Biocatalysts for the Solubil
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Results Enzyme Modification with Di
Page 163 and 164:
Conclusions Reducing enzymes can be
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Dynamics of the Extract Molecular-W
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where yi = (x-xi !/pi. The zero mom
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satisfactory agreement between theo
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0.8 0.6 0.4 0.2 “E \ bo Y, - 1 0
Page 173 and 174:
The Use of Solid State C-13 NMR Spe
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differences lie in the fact that th
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I- z W 0 K W n PROTONATED AROMATIC
Page 179 and 180:
ZAP WIO SIDE CHAINS IN PYRIDINE EXT
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ORGAFlIC VOLATILE MATER AND ITS SUL
Page 183 and 184:
(Figure 1). They indicated that the
Page 185 and 186:
Table 3. Elemental analysis of arom
Page 187:
1- 700'C Figure 3. GClFID chromatog
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