liquefaction pathways of bituminous subbituminous coals andtheir

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i ALIPHATIC PROTON STRUCTURAL PARAMATERS IN PYRIDINE EXTRACTS FROM ARGONNE COALS - Figure 7. Aliphatic proton srmctunl panmctm of the APCS coals. 654
ORGAFlIC VOLATILE MATER AND ITS SULFUR-CONTAINING COMPOUNDS PRODUCED BY COAL PYROLYSIS M.4.M. Chou, C.W. Kruse, and J.M. Lytle, Illinois State Geological Survey, Champaign, IL 61820 KK Ho, Illinois Clean Coal Institute, Carterville, IL 62918-0008 Keywords: coal, pyrolysis, volatile matter INTRODUCTION The types and distributions of the major components in the volatile matter produced from two types of coal pyrolysis were examined. Batch pyrolysis was used to produce coal tars for fractionation and characterization. Flash pyrolysis, in combination with gas chromatography (GC) analysis, showed a broad distribution of the volatile organics, including sulfurcontaining compounds. Further characterization of these volatile sulfur compounds should provide the understanding needed of coal's behavior during thermal processing, an understanding critical for cleaning coal through flash pyrolysis or thermal pre-treatment processes. EXPERIMENTAL Tar Collection, Separation, and Characterization - Batch Pyrolysis: About 100 g of coal was pyrolyzed at 450 'Cor 600 'C in a Parr reactor (1). The tar was delivered through a heated quartz tube to a collection flask containing a mixture of tetrahydrofuran and dimethoxypropane at -30 'C. After evaporation of the solvents, the tar was fractionated into acid, base, neutral-nitrogen, saturates, and aromatic fractions by ion- exchange, coordination, and adsorption chromatography (SARA) (2). The a-paraffins, separated from the saturates by a molecular sieve method (3), were analyzed by GC. Three solvents (5% benzene in pentane, 15% benzene in pentane, and 20% benzene/20% ethyl ether/60% methanol) were used to separate aromatic fractions into three subfraction by column chromatography on alumina. The fractions were designated monoaromatics, diaromatics and polyaromatics, and identified as SAF-1, SAF-2, and SAF-3, respectively (4). Elemental analyses were performed on each subfraction. On-line Analysis of Volatile Matter fmm Flash Pyrolysis: A Perkin-Elmer 3920B gas chromatograph (GC) with a flame photometric detector (FPD) and a flame ionization detector (FID) and a Dexsil-300 column (programmed for 8 'Chin from 50 'C to 280 'C) was used. Coal volatile matter was produced by a Chemical Data System pyroprobe 190 pyrolyzer in the GC's injection port. Pulverized coal (5 mg to 15 mg) in a 25 mm by 2.4 mm quartz tube was heated at 75 'C/msec in the GC's helium carrier gas flowing at 30mUmin. Samples were preheated at 100 'C for 30 seconds prior to the first analysis. A given sample was analyzedat 300 'C, 400 'C, 500 'C,600 'C, 700 'C, and 800 'C. The pyroprobe temperaturewas held at each temperature for 20 seconds and then it was allowed to return to the injection port temperature during the 37 minutes required for the GC analysis of the volatile matter from each step using the FID. A new coal sample was analyzed at 600 'C with FPD for sulfur compounds. RESULTS AND DISCUSSION Batch Pyrolysis Pruducts: The amount of tar obtained from the pyrolysis of six coals (Table 1) varied from 3 to 15 weight percent of the raw coal and the yields were approximately proportional to the H/C atomic ratio of the raw coal. Yields of fractions separated from each coal by the SARA method are also listed in Table 1. The aromatic fraction was generally the largest fraction in the tars. Elemental analysis of the SARA fractions from one coal sample (Table 2) showed most of the nitrogen to be in the base fraction. Sulfur was more evenly distributed but it too was highest in the base fraction. The C, H, N, and S contents of the three aromatic subfractions are listed in Table 3. The H/C ratio decreased as expected for a progression of increasing aromaticity from monoaromatics (SAF-I) to the polyaromatics (SAFJ). Sulfur in the aromatic fractions was detected only in the polyaromatic subfractions, and this trend was observed both at 450 'C and 600 'C. The nitrogen content within the aromatic subfractions varied in a similar fashion, especially at 600 'C. The lack of sulfur and nitrogen in the monoaromatics and diaromatics fractions may be due a higher ratio of the functional group(s) to carbon atoms in the hydrocarbon portion of the molecule, or to having both sulfur and nitrogen in the same small molecule. Either factor might result in the partitioning of these aromatics into earlier SARA fractions, 655
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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
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Apoaratus and Procedure Microflow R
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Model ComDound Test Figure 5 shows
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Figure 1. High resolution gas chrom
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Figure 5. Product distribution for
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THQ at somewhat higher temperatures
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areas of the particles and the SEM
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Experimental Catalyst Precursors an
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impregnating solvent. Table 3 shows
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of MoCo-TC2 at the level of 0.5 wt%
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Table 4. Effect of Temperature Prog
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In the past, chemical treatments in
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The effect of Corn20 preaatment on
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Reaction Time Figure 1 - Schematic
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DISSOLUTION OF THE ARGONNE PREMIUM
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A much more def~tive trend is seen
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EFFECT OF CHLOROBENZENE TREATMENT O
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same conditions and an extraction t
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ACKNOWLEDGEMENT The authors thank t
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THE STRUCTURAL &=RATION OF HUMINlTE
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to be originally derived from demet
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145 30 I --/---Jh I , , I I , 250 2
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THE EFFECTS OF MOISTURE AND CATIONS
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1 for the Zap lignite. These result
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content of the samples ion-exchange
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Table 1. F'yrolysis Results of Vacu
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585 I
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EFFECT OF TEMPERATURE, SAMPLE SI2E
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of some of the thermobalance runs.
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2. The mechanism of drying is a uni
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Influence of Drying and Oxidation 0
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"c gives W conversion mpared to the
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Table 1. Products dismbutions (dmmf
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- 50 45 40 E 35 2 30 E T) 25 ap 20
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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
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: ZAP WIO SIDE CHAINS IN PYRIDINE EXT
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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