Liquefaction co-processing of coal shale oil at - Argonne National ...

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in solvent power of the steam at a higher pressure, leading to reduced extraction. Twenty five experiments were performed in all. The conversions in Tables 3 and 3 represent average values for experiments at the same conditions. CHEMISTRY Extract and residue samples from two experiments, Runs 5 and 27, were analyzed by infrared spec- troscopy, NMR and'FIMS. Run 5 consisted of a 320 ' c pretreatment followed by a 430 * C treat- ment, while Run 27 was at 200 ' c and 400 ' c. Table 4 shows the elemental analyses of the extract and the residue of Run 27. The analysis of the feed coal is also shown for comparhon. The extract has a higher H/C ratio (1.28) a8 compared to the feed coal (0.95), whereas the residue has a lower ratio (0.68). The O/C ratio follows a similar pattern, being higher in the extract (0.32) than in the feed (0.28), and lower in the residue (0.13). The steam pretreatment/extraction process produces a hydrogen-rich extract which contains oxygenated compounds and heteroatomic species of the original coal, leaving behind a more condensed aromatic residue. The same trend is indicated lor nitrogen and sulfur, being enriched in the extract and reduced in the residue. But here because of the small.amounts, especially of nitrogen, accuracy in low. The infrared spectrum of the steam extract or Run 27 is shown in Figure 3. The IR spectrum is dominated by broad, strong -OH stretching vibrations in the 3400-3100 cm-' region. The presence of sharp aliphatic -OH hands just below 3000 cm-' suggests that the extract contains aliphatic material, and reinforces the observed enrichment of H and 0 in the extract. Further confirmation is provided by the 'H NMR spectrum of the steam extract from Run 5 shown in Figure 4. The ratio 01 H,,/H,,, is 1:30. 43% of the H,,, hydrogens are associated with methylene, methine, or methyl groups which are not directly bonded to aromatic nuclei. Another 20% 01 the Kat appearing as a group of signals in the 2-3 ppm region are associated with hydroaromatic structures or associated with methyl, methylene and methine groups directly attached to an aromatic nucleus. The dominant sharp signal at 1.2 ppm is characteristic of long chain polymethylene groups. Thus, one of the major constituents of the hydrogen rich extract is aliphatic8 present primarily as long chain polymethylenes, either as free species or attached to aromatic/hydroaromatic ring systems. The NMR spectrum (Figure 5) is dominated by a number of well resolved lines riding on a spectral envelope in the 15-80 ppm region which in the normal chemical shift region for aliphatic compounds, supporting the presence of signitlcant quantities of aliphatic materials in the steam extract. The most intense signal is at 30.2 which is generally assigned to the internal methylene carbons (c~-c~-c~-cn-) of straight chain alkanes corroborating the presence of long chain polymethylene groups (minimum average carbon chain length; nc+?-lO) which may or may not be attached to an 324
I I aromatic ring. The group of signals in the 1520 ppm region is probably due to the methylene carbons attached to aromatic rings. The presence of a broad spectral envelope in addition to the sharp alkane lines demon- strate the extract's complexity. The spectral complexity is due to the presence of small amounts of polymethylene type compounds. The complex band of carbon signals in the 120-130 ppm region is due to the aromatic and polycyclic aromatic species. Interestingly, a small, but distinctive signal occurs at 179 ppm which is whpre the carbonyl carbon of a -COOH group appears suggesting the presense of some carboxylic acids in the extract. Field ionization mass spectomety (FIMS) M a mass spectometry technique which uses a soft ionization mode and allows most molecules to be observed as unfragmented molecular ions. The method can provide a true molecular weight profile for any given complex mixture. Figure 6 represents the field ionization mass spectrum of the extract. The extract has a very narrow molecular weight distribution witb number average (M,) and weight average (M,) molecular weight of 315 and 373, respectively. Since 75% of the material was volatilized in the FIMS probe the observed molecular weights are a true representation of the extract and the extract is composed of low molecular weight compounds. The most prominent peaks in the spectrum appear at m/z 110, 124, and 138 and can be assigned to dihydroxyl benzene and its methyl and ethyl analogs, respectively. Suprisingly no prominent peaks due to monohy- droxyl benzene (phenol) or its C-1 or C-2 analogs are found. The oxygenated compounds present in tbe extract are best represented by the clabs of dihydroxyl benzenes and other dihydroxyl aromatics. There are a number of other prominent peaks in the higher molecular weight range which, in all probability, arise from the polymethylenes attached to an aromatic ring (identified by NMR) but the FIMS analysis does not allow ready identification of these compounds. Tbe presence of reactive components like the polymethylene species, the dihydroxyl benzenes, and tbe low molecular weight profile of the extract sugkests that the coal is very reactive and not a highly condensed, very large molecular weight, intractable molecule. Self condensation and crosslinking reactions of the dihydroxyl aromatics, alkylation of the activated aromatic rings by the polymethylene species in the coal , are some of the retrogressive reactions that these coals can undergo, under the severe processing conditions generally employed. Pretreatment witb steam, at lower temperatures, allows the breaking of hydrogen bonds, loosening up the coal matrix, and stabilizing some of the reactive components in the coal. When the temperature increases during the supercritical extraction step, many of these reactive molecules can be steam volatilized or steam extracted, escaping the loosened coal matrix structure before undergoing retrogressive reactions. This explanation is supported since the introduction of a low temperature pretreatment step before the supercritical steam extraction leads to a 32% increase in conversion. The presence of reactive dihydroxyl benzenes in the extract is also supporting evidence. Dihydroxyl aromatics have never been reported M occuring in coal liquids obtained under normal coal processing 325
Page 1 and 2:
ABSTRACT LIQUEFACTION CO-PROCESSING
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eaction temperature, 1000-1500 psig
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6. 7. 8. 9. 10. 11. 12. 13. 14. 15
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I 0" 100- I I I WyO-3 P 3: 1500 psi
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11.3 A-6 yJ 600 OF, 1500 psig CO, 3
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Experimental UDqradinq and Cooroces
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catalytic to the thermal hydrogenat
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the reaction with oil production re
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TET did not promote the production
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MICROAUTOCLAVE DESCRIPTION AND PROC
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FEEDSTOCK PROPERTIES Some propertie
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CONCLUSIONS HRI's microautoclave ha
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176
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100. 2 8%. M = ?8. 38. .... . . . .
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CATALYTIC CO-PROCESSINS OF OHIO NO.
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CATALYST COMPARISON STUDY The premi
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fractions and a decrease of heavier
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TABLE 2 Coal Analyses I1 1 i noi s
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Temperature WHSV, G/hr/cc TABLE 6 C
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z FIGURE 3 COAL REACTIVITY SCREENIN
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COPROCESSING USING HzS AS A PROMOTE
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- 3 - that product yields depend on
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- 5 - occurs in the yields of aspha
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Table 1 Analysis of Feedstocks Fore
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THO-STAGE COPROCESSING OF SUBBITUMI
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esult in retrogressive reactions ta
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8. 6. Ignasiak, L. Lewkowicz, G. Ko
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Table 4 OVERALL MASS BALANCE FOR TH
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BACKGROUND COAL LIQUEFACTION/RESID
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system, which could be operated wit
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TABLE 1 EFFECT OF LC-FINING~"' TEMP
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Figure 1. SCHEMATIC OF LCI CO-PROCE
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SIMULATION OF A COAL/PETROLEuII RES
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20 pseudocomponents was developed t
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ottoms is less sensitive to the num
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Low Pressure Separator A temperatur
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7. Gallier, P.W., Boston, J.F., Wu,
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I I I I I I I I I 100- --- Experime
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Coprocessing Schemes The coprocessi
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processing 25,000 and 150,000 bbl/d
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FIGURE 1 I DISTRIBUTION OF REFINERI
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Table 1. Samples Analyzed PNLNumber
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the coal itself. The chemical compo
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- - ITSL PAH Fraction PAH Fraction
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PROCESS DEVELOPMENT STUDIES OF TWO-
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SUMMARY e The major effect of close
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omw '??h 4NO WNID ?N? 000 wmm c9'1'
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tl f 246
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248
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qkCqQ r! o! 0 0 0 0 0 0 0 I-UH ')I
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Materials The catalyst was shell 32
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CONCLUSIONS Separation of a light h
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Table 3. Results of activity testin
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feed coal and plant configuration a
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P1 #2 #3 114 115 #6 ITSL subbitumin
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temperature, time and solvent power
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TABLE 1 EXPERIMENTAL CONDITIONS AND
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la Figure 1. lH-NMR spectra of samp
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PERFORMANCE OF THE LOW TEMPERATURE
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BENCH UNIT DESCRIPTION Process deve
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Recycle Residuum Hydrogenati On Res
Page 123 and 124: FIRST STAGE HRI'S CATALYTIC TWO STA
Page 125 and 126: FIRST-STAQ COAL CONVERSION (W I IIA
Page 127 and 128: REACTOR SOLIOS HTOROGEN/CARBON ATOl
Page 129 and 130: TRANSPORTATION FUELS FROM TWO-STAGE
Page 131 and 132: Process Identification LV% Of AS- R
Page 133 and 134: Table I11 HYDROTREATING TESTS WITH
Page 135 and 136: Table IV HYDROTREATING TO 0.2 PPM N
Page 137 and 138: Table VI EFFECT OF BOILING RANGE ON
Page 139 and 140: (4) In all cases studied, the jet f
Page 141 and 142: 292
Page 143 and 144: INTEGRATED TWO-STAGE LIQUEFACTION:
Page 145 and 146: are over-riding features in its fav
Page 147 and 148: Complementary fundamental studies o
Page 149 and 150: Comparative Economics of Two-Stage
Page 151 and 152: The variation in hydrotreating cost
Page 153 and 154: FIGURE 1: COMPARISONS OF ILLINOIS N
Page 155 and 156: Process TABLE 1: TWO-STAGE PROCESSE
Page 157 and 158: Abstract Temperature-Staged Catalyt
Page 159 and 160: Results and Discussion Reactions in
Page 161 and 162: 2. 3. 4. 5. 6. Derbyshire, F. J. an
Page 163 and 164: I LL a rJJW ., .. ;> 0 i s W 8 a 31
Page 165 and 166: Materials Feeds to the WGS-solvent
Page 167 and 168: products. Thus, coupling the WGS an
Page 169 and 170: 5. R. J. Xottenstette, Sandia Natio
Page 171 and 172: ENHANCED COAL LIQUEFACTION WITH STE
Page 173: change in weight being compared to
Page 177 and 178: T,\llI.l< I ASAI,YSIS OP \\YOl)Al\:
Page 179 and 180: 00 3000 2000 le00 1600 1400 1200 IO
Page 181 and 182: THE EFFECT OF REACTION CONDITIONS O
Page 183 and 184: and may ultiontely form methyl-subs
Page 185 and 186: ! 5. Narain, N.K., Utz, B.R., Appel
Page 187: 4 (u I t + 9 (u I 337 - Q 0
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