liquefaction pathways of bituminous subbituminous coals andtheir

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Table 5. Summary of Estimated Coefficients' Inter- Tb Xb cept Coef f Coef f (PI + THF 107.40 4.54 4.08 -1.72 -1.62 Conv (. 003) (. 005) (. 097) mg H2 60.28 9.12 2.66 -1.13 (. 001) (. 014) ( .097) HC Gas 3.50 1.86 ( .001) (.061) CO+C02 5.06 0.84 -0.20 ( .001) ( .046) TGas 8.57 2.71 (. 001) Oils 58.61 13.87 ( .001) -12.03 4.80 ( .005) ( .085) L (. 169) a. All three way interaction coefficients (TxXxS) are small and set equal to zero. Coefficient estimates are for coded variables (-l,O,+l). b. T = temperature; X = wt% Fe in SFIO on coal; S = wt% sulfur in DMDS on coal; TxX = two-way interaction of temperature with wt% Fe in SFIO on coal; TxS = two-way interaction of temperature with wt% sulfur in DMDS on coal; XXS = two-way interaction of wt% Fe in SFIO with wt% sulfur in DMDS on coal. Table 6. Comparison of Wilsonville and Superfine Iron Oxide' Fe, wt % coal Yields, wt% maf coal HC Gases co+c02 oils Thermal None 1.9 5.0 48.5 WIO Predictedb Experimental SFIO SFIO 1.1 1.1 1.1 2.1 2.6 1.2 4.8 4.9 5.0 53.8 63.7 56.9 PA+A 52.2 45.3 35.1 45.1 IOM -7.6 -6.0 -6.3 -8.2 THF COnV. 107.6 106.0 106.3 108.2 Run Number 13 -11167-1 14 -21189-1 N/A 272-1 a. 415'C. 1 hour, 1000 psig H2 cold, 5.4 grams Wilsonville recycle oil, 3.0 grams coal, 2.4 moles sulfurlmole iron. b. Predicted from model parameters. All curvature detected at the mid-range conditions is accounted for as resulting from temperature effects. 502
EFFECT OF A CATALYST ON THE DISSOLUTION OF BLIND CANYON COAL Robert P. Warzinski U.S. Department of Energy Pittsburgh Energy Technology Center Pittsburgh, PA 15236 Keywords: coal liquefaction, dispersed catalyst, molybdenum hexacarbonyl INTRODUCTION The use of catalysts to improve the dissolution and liquefaction of coal dates back to the 1920s. Reviews in this area have been prepared by Weller (11, Derbyshire (21, and Anderson (3). Recently, interest has been renewed in using dispersed catalysts in the early phases of coal liquefaction to improve the quality of the products produced during the initial dissolution and liquefaction of coal. To facilitate the study of dispersed catalysts in laboratory-scale investigations, a particular sample of 'Blind Canyon coal (denoted DECS-17) that contains very low levels of pyrite (0.04 wt% on a moisture-free basis) has been made available by the Department of Energy through the Penn State Coal Sample Bank. Thus, complications due to inherent catalytic activity associated with pyrrhotites which can be formed from coal pyrite are eliminated and interferences to the characterization of the added catalysts due to native iron and sulfur are reduced. The purpose of this paper is to define the effects of a molybdenum-containing catalyst on the initial dissolution and conversion of the DECS-17 coal as a function of temperature. To eliminate competing andlor complicating influences of added solvents, the liquefaction tests were performed in the absence of such materials. The catalytic effects on coal conversion and gas uptake were determined by subtraction of thermal data from the corresponding catalytic results at a given temperature. The results provide a picture of the reactivity of the DECS-17 coal and its response to a dispersed liquefaction catalyst. EXPERIMENTAL All of the experiments were performed with the DECS-17 Blind Canyon coal from the Penn State Coal Sample Bank. The coal was minus-60 mesh and was riffled prior to use. The elemental analysis (on a dry basis) provided with the coal was as follows: 76.3% carbon, 5.8% hydrogen, 1.3% nitrogen, 0.4% sulfur, 6.6% ash, and 9.7% oxygen (by difference). The moisture content of the as-received coal was 3.7%. The liquefaction tests were conducted in 31 6 stainless-steel microautoclaves. The total internal volume, including connecting tubing, of the microautoclave used in most of this work was 49.0 cm3. During the tests, the microautoclave was mounted in a horizontal position and shaken in an arc motion at approximately 360 cycles per minute in a heated, fluidized sand bath. The microautoclave was charged with 3.3 g of coal and, if used, 0.008 g of molybdenum hexacarbonyl, Mo(CO),. The Mo(CO), was used as received from Strem Chemical Company. Purity was given as 98 + YO with moisture being the only major contaminant. No special procedures were used to mix the Mo(CO), with the coal; the compound was simply added from a spatula directly to the microautoclave containing the coal sample. 503
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
Page 11 and 12: 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: Table 3. Effect of Superfine Iron O
Page 31 and 32: inherent volatility of Mo(CO), perm
Page 33 and 34: Analysis of the quantity and compos
Page 35 and 36: $ EO .- 0 m L 0 c 0 0 > 40 300 350
Page 37 and 38: 0 0 0 0 0.000 0.005 0.010 0.015 0.0
Page 39 and 40: 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
Page 45 and 46: - iF m 1.6 1.4 1.2 - - - 1- 0 0.8 -
Page 47 and 48: RESULTS AND DISCUSSION Swelling of
Page 49 and 50: . . % . . 9 'HF 0 0 0 *. . 0 . . 0
Page 51 and 52: 1.50 KQ 1.00 0.50 I / ' 02 525 I 1
Page 53 and 54: hydrogen atoms. The hydrogen atoms
Page 55 and 56: 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
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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 and 112:
585 I
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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
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- 50 45 40 E 35 2 30 E T) 25 ap 20
Page 127 and 128:
Influence of Drying and Oxidation o
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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
Page 163 and 164:
Conclusions Reducing enzymes can be
Page 165 and 166:
Dynamics of the Extract Molecular-W
Page 167 and 168:
where yi = (x-xi !/pi. The zero mom
Page 169 and 170:
satisfactory agreement between theo
Page 171 and 172:
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
Page 175 and 176:
differences lie in the fact that th
Page 177 and 178:
I- z W 0 K W n PROTONATED AROMATIC
Page 179 and 180:
ZAP WIO SIDE CHAINS IN PYRIDINE EXT
Page 181 and 182:
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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