liquefaction pathways of bituminous subbituminous coals andtheir

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I I s F B 1: 8 a cc 30 40 50 60 70 80 CO evolved before 750°C (%of total CO) ""L3 10 n - 10 20 30 Total CO evolution (wt% dat7 Correlation of P olysis Tar %%%rand oluene Soluges from Li uefaction 2) for Zap Lpte with, a)(hyrolysis COEvoluhon efore 750 C; b) Total Pyrolysis CO Evolution. Time (minutas) h Time (minutes) Time (minutea) (minutas) Figme 4. CO Evolution Dunn Coal P olysis. a) Raw Zap; b) Remoisturized Zap; c) aw Wyodal?; d) Remoistunzef Wyodag 586
EFFECT OF TEMPERATURE, SAMPLE SI2E AND GAS FLOW RATE ON DRYING OF BEULAH-ZAP LIGNITE AND WYODAK SUBBITUMINOUS COAL Karl S. Vorres Chemistry Division, Building 211 Argonne National Laboratory Argonne, IL 60439 Keywords: drying, liquefaction, TGA ABSTRACT Beulah-Zap lignite and Wyodak-Anderson (-100 and -20 mesh from the Argonne Premium Coal Sample Program) were dried in nitrogen under various conditions of temperature (20-80°C), gas flow rates (20-160 cc/min), and sample sizes (20-160 mg). An equation relat- ing the initial drying rate in the unimolecular mechanism was developed to relate the drying rate and these three variables over the initial 80-85% of the moisture loss for the lignite. The behavior of the Wyodak-Anderson subbituminous coal is very similar to that of the lignite. The nitrogen BET surface area of the subbituminous sample is much larger than the lignite. INTRODUCTION Economical production of synthetic coal liquids suitable for transportation fuels is a continuing goal of a number of coal conversion programs. The vast reserves of low rank coals in the western part of the U. S. provide a plentiful supply of input for potential processes. The low rank coals generally possess a high reactivity in many chemical reactions which also make them attractive feedstocks. One of the major detractors, however, is the high moisture content associated with many of these fuels, ranging up to 40%. An economical means of removing the moisture without sacrificing the reactivity or oil yields would be desirable. A number of studies have been carried out on the drying behavior of coals from a fundamental viewpoint (1,2,3,4,5). The drying behavior has been found (1,2,3,4) to follow a unimolecular mechanism in a flow of dry gas (nitrogen or carbon dioxide) over a range of temperatures, gas flow rates and sample sizes). The mechanism proceeds through two stages. The initial stage accounts for about 80-85% of the moisture loss, while the second accounts for all but about 1% of the rest of the loss. EXPERIMENTAL Coal drying was done with a modified Cahn model 121 thermobalance or thermo-gravimetric analyzer (TGA) attached to an IBM PC/XT microcomputer. Vendor-supplied software was used to monitor the progress of individual runs, and convert data files to a form that could be further studied with Lotus 123. The data were obtained as files of time, temperature and weight at 10 second intervals. Run times varied from 7-23 hours. Sample sizes typically started at about 80 mg, but varied from 587
Page 1 and 2:
LIQUEFACTION PATHWAYS OF BITUMINOUS
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the conversion of A+P and O+G with
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Asphaltcncs PrCasphaltenCS Cwr%, da
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NEW DIRECTIONS TO PRECONVERSION PRO
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ecause of incorporation of the coal
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should be considered more. The step
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17 18 Run no. 0 cys I ToS-CyS TS-To
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INTRODUCTION Effects of Thermal and
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apid decline in modulus. The loss m
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-0.01- . 04 5 -0.03- E 6 -0.0s- c)
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Assessment of Small Particle Iron O
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yields are calculated by subtractin
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conversion is greater than the corr
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Table 3. Effect of Superfine Iron O
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EFFECT OF A CATALYST ON THE DISSOLU
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inherent volatility of Mo(CO), perm
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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
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Different levels of adsorption occu
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Nominal 2 Table 1. Concentration of
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- iF m 1.6 1.4 1.2 - - - 1- 0 0.8 -
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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
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12. a. Poutsma, M. L.; Dyer, C. W.
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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 and 108: content of the samples ion-exchange
Page 109 and 110: Table 1. F'yrolysis Results of Vacu
Page 111: 585 I
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
Page 161 and 162: Results Enzyme Modification with Di
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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
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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
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ZAP WIO SIDE CHAINS IN PYRIDINE EXT
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ORGAFlIC VOLATILE MATER AND ITS SUL
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(Figure 1). They indicated that the
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Table 3. Elemental analysis of arom
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1- 700'C Figure 3. GClFID chromatog
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