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

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eaction, the platform was lowered and the microreactor was cooled with a stream of room-temperature air. The outside of the cooled microreactor assembly was cleaned (to remove sand) with compressed air. Gases were vented, and the microreactor was disassembled. The reacted suspension was pipetted into a 50-mL volumetric flask containing 0.100 gm durene and 0.100 gm fluorenone, which were the internal standards used for quantitative capillary gas chromatography, The remaining residue and synthetic solvent in the microreactor were removed with tetrahydrofuran (THF) and added to the flask. Aliquots were then analyzed using a 50-meter highly cross- linked phenylmethylsilicone capillary column. Flame ionization was used to detect individual components of the treated synthetic solvent, although in certain instances a mass-selective detector was also used to assist in the identification of products. Solvent loss of each component was determined by calculating the difference between the original amount of the component and the recovered amount of the component and its reaction by-products. Solvent that was lost and unaccounted for represented adducted or polymerized material. A l l percentages will be discussed on an absolute basis; therefore, the loss of 10% tetralin would represent 10% of the synthetic solvent and not 10% of the 20% tetralin present in the synthetic solvent. The solvent losses would be five times larger if they were based on the weight of the coal sample, since the so1vent:coal ratio was 5:1, i.e., loss of 3% of the solvent by adduction would represent a 15% addition to the weight of the coal. RESULTS AND DISCUSSION The effect of reaction conditions on solvent loss, and specifically on pref- erential loss of components of the solvent, was examined at three sets of reaction conditions. Experiments were conducted under SCTL conditions (rapid heat-up, 3 min at 425OC). traditional conditions (gradual heat-up, 30 min at 425OC), and severe conditions (gradual heat-up, 6 hours at 425OC). The advantages in using this synthetic solvent are that all components of the solvent are known, its elemental composition is similar to a coal-derived recycle solvent, and the multi- component solvent simulates a recycle solvent better than a one-component solvent does. The use of a synthetic solvent also allows the study of individual components in a more realistic environment. The objective was to examine solvent recovery with increasing severity of coal-liquefaction reaction conditions, The SCTL stage of an ITSL process involves rapid heat-up, followed by a short residence time at reaction temperature. During rapid heat-up, the rate of free-radical production should increase significantly in a SCTL stage. An increase in free-radical concentration was hypothesized, since the demand for hydrogen, with increased free-radical production, would increase and would be less likely satisfied by hydrogen donors and gaseous hydrogen. With an increase in free-radical concentration, a concomitant increase in solvent adduction was hypothesized, since free-radical addition, aromatic sub- stitution, and polymerization reactions involving solvent and coal free-radicals xould be likely. In comparing results obtained under SCTL conditions (Table 1) with results obtained from experiments conducted under traditional liquefaction conditions (gradual heat-up to 425OC, 30 min at 425OC), solvent loss due to adduction should also be occurring under traditional conditions. As the severity of the liquefaction conditions is increased, adducted solvent should undergo cleavage (cracking, hydrogenolysis, etc. ) and re-form solvent-like products, resulting in improved solvent balance. While the original components may not be recovered, products having similar structures and chemical properties should be. For example, adduction of phenanthrene with a coal-derived benzylic radical may occur 332
and may ultiontely form methyl-substituted phenanthrene (Figure 1). Baaed on this hypothesis, severe solvent loss uas expected uith a SCTL process compared to moderate solvent loss under traditional liquefaction conditions, and if the conditions were severe enough, solvent that was initially adducted, or solvent-like products, could be recovered. Results from SCTL reactions demonstrated that components of the synthetic solvent were not adducted, degraded, or lost. While 755-855 of the coal was con- verted to THF-soluble material, only 2.61 tetralin underwent dehydrogenation. No adduction of m-cresol or quinoline uas observed. Results wing a synthetic solvent demonstrate that SCTL is a favorable process because solvent balance with little solvent degradation can be achieved. These results were unexpected and suggest that an increased concentration of free radicals in a short period of time does not cause solvent loss or degradation uhen sufficient readily donable hydrogen is present. The results also imply that free radical production does not play an important role in solvent loss via adduction. It should also be understood that little, if any, of the recovered, original solvent components are coal-derived. Based on coal experiments performed uith one- and two-component solvents, negligible quantities of quinoline, m-cresol, and 1-methylnaphthalene could be considered coal-derived, while a maximum of 0.2% tetralin, 0.3% naphthalene, 0.2% pyrene, and 0.1% phenanthrene were coal-derived. Experiments conducted using traditional coal liquefaction reaction conditions shoued that solvent balance could still be achieved, but degradation of the solvent had started to occur. Results from experiments performed in the absence of coal showed that little, if any, demethylation and decomposition of 1- methylnaphthalene had occurred. Reactions in the presence of coal showed that approximately 3.21 l-mthylnaphthalene had undergone demethylation and decomposition. Some of the demethylated product (2.2%) could be accounted for by the increased amounts of naphthalene. Tetralin reactions included dehydrogenation to naphthalene (6. l%), rearrangement to 1-methylindane (0.5%), and decomposition to butylbenzene (0.1%). The total amount of tetralin and its reaction products is 22.2%; therefore, the additional amount (based on 20% tetralin in the synthetic solvent) could be accounted for by demethylation of 1-methylnaphthalene. It is possible that more than 2.2% 1-methylnaphthalene underwent demethylation to naphthalene if tetralin was being lost via unidentified reactions and not via dehydrogenation to naphthalene. If this occurred, then greater amounts of recovered naphthalene could be attributed to the demethylation of 1- methylnaphthalene and not to the dehydrogenation of tetralin. Methylation was also occurring, and 0.4% dimethylnaphthalene and 0.3% dimethylphenol were pro- duced. Hydrogenation of the aromatic components was also occurring, producing 1.03 methyltetralin, 1.7% dihydrophenanthrene, 0.1% tetrahydrophenanthrene, 0.8% dihydropyrene, and 1.3% tetrahydroquinoline. The production of methyltetralin is most likely occurring via the hydrogenation of 1-methylnaphthalene, since no methylation of tetralin was observed when blank experiments using tetralin as a solvent were conducted. The major degradation reactions occurring were rearrangement of tetralin to 0.5% 1-methylindane (Equation 1 ) and cracking to butylbenzene (0.1%). H HU H 333
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
Page 45 and 46:
- 5 - occurs in the yields of aspha
Page 47 and 48:
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
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FIRST STAGE HRI'S CATALYTIC TWO STA
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FIRST-STAQ COAL CONVERSION (W I IIA
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REACTOR SOLIOS HTOROGEN/CARBON ATOl
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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 and 174: change in weight being compared to
Page 175 and 176: I I aromatic ring. The group of sig
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: THE EFFECT OF REACTION CONDITIONS O
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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