liquefaction pathways of bituminous subbituminous coals andtheir

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100 3 E2 Untreated IIII M~OH/HCI C O ~ O 'I ................................................... WY ND IL PITT Figure 2 - Effect of Pretreatment with MethanoVNydrochloric acid and Carbon Dioxidemater on Low Severity Liquefaction Reactivity of Argonne Coals 1 nn v) Untreated MeOWHCl CO&O 'I - I 1 80 4 ...................................................................................... ad B !f 60 v 8 40 g 8 20 E b 0 .................................................................... I ................. UT wv UF POC Figure 3 - Effect of Pretreatment with MethanoVNydrochloric acid and C&on DioxideNater on Low Severity Liquefaction Reactivity of Argonne Coals 560
DISSOLUTION OF THE ARGONNE PREMIUM COAL SAMPLES IN STRONG BASE* R. E. Wim, R. L. McBeth, and J. E. Hunt Chemistry Division. 9700 S Cass Avenue Argonne National Laboratory, Argonne, IL 60439 Keywords: Solubilization, Base Hydrolysis, Premium &als INTRODUCTION The objective of this study is to solubilize the Argonne Premium Coal Samples in order to facilitate analysis by mass spectrometry, FTIR and NMR. Earlier, in a search for relatively mild methods for solubilizing coal. we discovered that treating coals with potassium hydroxide in ethylene glycol at 250°C to be quite an effective approach.' Under these conditions, secondary reactions which may obscure the distribution of the basic building blocks of the coal slructure are not expected to occur. At higher temperatures. such as those used in more traditional liquefaction processes (> 400 "0, secondary reactions such as the formation of polycyclic aromatic and heteroaromatic compounds dominate. A focus of our approach to characterization of coals is desorption-pyrolysis high resolution CI and E1 mass spectrometry and laser desorption mass spectrometry (LDMS). It has been shown by PyMS that the yields and the distribution of products is superior for coal extracts compared to the original whole coals.u There appears to be few secondary reactions occurring and many molecules. which are released in analysis of the extract, are trapped in the solid matrix of the coal and never observed. In sddition, soluble materials are more amenable to LDMS! The glycol/KOH system was chosen since in early work up to 93% of the product was soluble for lower- nnk bituminous coals.' Others have solubilized coals under basic conditions. &chi and co-workers' used ethanolic - NaOH at temperatures ranging from 260 "C to 450 "C. More recently, Stock and co-workers have discussed the use of Lochmann's base (potassium tert-butoxide, n-buty1 lithium in heptane at reflux) which is especially effective for the higher rank coals!J Also, a base hydrolysis is included in a low severity liquefaction scheme devised by Shabtai and co-workers? Table VII-I . Elemental analyses for the coal samples. %C Per 100 Carbons Sample Name (dmmf) H N S 0 8 Beulah-Zap Lignite 74.1 79.5 1.35 0.36 20.9 2 Wyodak-Anderson SubB 76.0 85.6 1.28 0.23 18.0 3 Henin hvCB 80.7 n.2 1.51 1.15 13.0 6 Blind Canyon hvBB 81.3 85.7 1.67 0.17 10.8 4 F'ittsburghhvAB 85.0 76.7 1.69 0.40 7.96 7 Lewiston-Stockton hvAB 85.5 76.3 1.62 0.30 8.93 I Upper Freepon mvB 88.1 66.0 155 0.32 6.59 5 Pocahontas IvB 91.8 58.5 1.25 0.21 2.04 561 "
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
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: Reaction Time Figure 1 - Schematic
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 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
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for determining the area of the pea
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of the ronl roniponcnte nnd (2) the
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2w 180 160 9 140 120 P loo f 80 P O
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25 I 20 ' + 0 Drying lime, hours Fi
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substructure have been identified a
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Pyridine extraction showed that 60
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Figure 1. Reflected white-light pho
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Table 3. Pyridine Extraction Sample
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A bang-bang control strategy was us
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increased from 120°C to 135”C, r
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* wt% based on the amount of naphth
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Use of Biocatalysts for the Solubil
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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
Page 185 and 186:
Table 3. Elemental analysis of arom
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1- 700'C Figure 3. GClFID chromatog
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