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

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separation. The high quality of the separations of the aliphatic hydrocarbons and PAC fraction is indicated by the much higher H/C ratio of the aliphatic fraction (1.70) compared to the PAC fraction (1.16) and the low concentrations of nitrogen and oxygen in these two fractions. In contrast, the N-PAC and HPAH fractions both have significant amounts of' oxygen and nitrogen indicating the presence of compounds that contain both heteroatoms or possibly some overlap of the fractions. Results of analyses of the aged catalysts, given in Table 2, show that catalytic hydrotreating of the aliphatic and PAC fractions yielded lower carbon accumulations on the catalysts than hydrotreating the V-178 or the N-PAC and HPAH fractions. Likewise, the catalysts used to hydrotreat the N-PAC and HPAH fractions have significantly higher accumulations of nitrogen than the catalysts used to hydrotreat the aliphatics and the PAC fractions. The 0.6 and 0.5 wt% accumulations resulting from our two hour experiments are comparable to the levels (0.5 to 0.6 wt%) observed on the first catalysts, with catalyst ages of about 20 lb resid/lb catalyst, withdrawn from Wilsonville runs. These results show that the nitrogen buildup on the catalyst under process conditions must be very rapid. Hydrogenation Activity The measured intrinsic activity losses (a) and the measured remaining extrudate activities (F) are given in Table 3. A quantitative mathematical expression, reported previously (E), relates F to a and effective diffusivity. Use of this equation enabled us to determine the catalyst effective diffusivities. The catalysts used to hydrotreat the V-178 and the aliphatic hydrocarbon and PAC fractions showed a 20% decrease in effective diffusivit from the fresh catalyst value of 5x10-6 cm2/sec/cm3, whereas those used to hydrotreat the HPAH and N-PAC fractions had greater than a 50% decrease. Recalculating the F values without these changes in effective diffusivity (i.e. with fresh catalyst effective diffusivity) (Table 3 ) shows that less than 10% of the loss of fresh extrudate activity is due to the changes in effective diffusivity. The relationship between F (corrected for changes in effective diffusivity) and a also enabled us to differentiate the two limiting modes of deactivation -- homogeneous and shell- progressive poisoning. A plot of F vs a for the results from the hydrogenation activity testing of the V-178 and the four chemical classes is shown in Figure 1. Since the a values increase more rapidly than the F values, the dominant mode of deactivation for these catalysts is homogeneous poisoning of active sites (9). As can be seen in Figure 1, the aliphatic hydrocarbons and the PAC fraction caused less deactivation than the V-178, whereas the N-PAC and HPAH caused more deactivation. This trend in deactivation is inversely correlated with the carbon contents of the aged catalysts given in Table 2. The catalysts used to process the aliphatics and the PAC fraction have lower carbon contents than the catalyst used to hydrotreat the V-178, whereas the catalysts used to hydrotreat the N-PAC and HPAH fractions have higher carbon contents. Hydrotreating the N-PAC fraction yields the greatest deactivation with about an 87% loss of extrudate hydrogenation activity and 98% of the active sites poisoned. 253
CONCLUSIONS Separation of a light hydrotreater process stream into four chemical classes has shown that about half of the stream is composed of aliphatic hydrocarbons. There are also small amounts of N-PAC and HPAH fractions. Hydrotreating each of these four fractions and the whole process stream with catalyst has shown that all four fractions cause deactivation. The greatest deactivation is due to the N-PAC fraction, although the HPAH fraction also yields greater deactivation than the whole process stream. The deactivation is caused primarily by active site poisoning, with a lesser amount due to a decrease in effective dif fusivity. REFERENCES 1. 2. 3. 4. 5. 6. 7. 8. 9. Ocampo, A., Schrodt, J. T. and Kovach, S. M., Prod. Res. Dev. 17(3), 266, 1978. Ind. Eng. Chem. Furimsky, E., Erzl Kohle, Petrochem %(E), 383, 1979. Stohl, F. V. and Stephens, H. P., Proc. Tenth Annual EPRI Contractors' Conference on Clean Liquid and Solid Fuels, April 23-25, 1985, Palo Alto, CA. Stephens, H. P. and Stohl, F. V., ACS Division of Fuel Chemistry Preprints 29(6), 79, 1984. Stohl F. V. and Stephens, H. P., ACS Division of Fuel Chemistry Preprints 30(4), 148, 1985. Lamb, C. W., Lee, J. M., Moniz, M. J., Risbud, H. M., Johnson, T. W., Proc. Tenth Annual EPRI Contractors' and Conference on Clean Liquid and Solid Fuels, April 23-25, 1985, Palo Alto, CA. Later, D. w., Lee, M. L., Bartle, K. D., Kong, R. C. and Vassilaros, D. L., Anal. Chem. 53, 1612, 1981. Stephens, H. P. and Stohl, F. V y ACS Division of Petroleum Chemistry Preprints 30(3), 465, 1985. Wheeler, A., Catalysis 2, 105, P.H. Emmett ed., Reinhold, N.Y., 1955. 254
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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
Page 51 and 52: esult in retrogressive reactions ta
Page 53 and 54: 8. 6. Ignasiak, L. Lewkowicz, G. Ko
Page 55 and 56: Table 4 OVERALL MASS BALANCE FOR TH
Page 57 and 58: BACKGROUND COAL LIQUEFACTION/RESID
Page 59 and 60: system, which could be operated wit
Page 61 and 62: TABLE 1 EFFECT OF LC-FINING~"' TEMP
Page 63 and 64: Figure 1. SCHEMATIC OF LCI CO-PROCE
Page 65 and 66: SIMULATION OF A COAL/PETROLEuII RES
Page 67 and 68: 20 pseudocomponents was developed t
Page 69 and 70: ottoms is less sensitive to the num
Page 71 and 72: Low Pressure Separator A temperatur
Page 73 and 74: 7. Gallier, P.W., Boston, J.F., Wu,
Page 75 and 76: I I I I I I I I I 100- --- Experime
Page 77 and 78: Coprocessing Schemes The coprocessi
Page 79 and 80: processing 25,000 and 150,000 bbl/d
Page 81 and 82: FIGURE 1 I DISTRIBUTION OF REFINERI
Page 83 and 84: Table 1. Samples Analyzed PNLNumber
Page 85 and 86: the coal itself. The chemical compo
Page 87 and 88: - - ITSL PAH Fraction PAH Fraction
Page 89 and 90: PROCESS DEVELOPMENT STUDIES OF TWO-
Page 91 and 92: SUMMARY e The major effect of close
Page 93 and 94: omw '??h 4NO WNID ?N? 000 wmm c9'1'
Page 95 and 96: tl f 246
Page 97 and 98: 248
Page 99 and 100: qkCqQ r! o! 0 0 0 0 0 0 0 I-UH ')I
Page 101: Materials The catalyst was shell 32
Page 105 and 106: Table 3. Results of activity testin
Page 107 and 108: feed coal and plant configuration a
Page 109 and 110: P1 #2 #3 114 115 #6 ITSL subbitumin
Page 111 and 112: temperature, time and solvent power
Page 113 and 114: TABLE 1 EXPERIMENTAL CONDITIONS AND
Page 115 and 116: la Figure 1. lH-NMR spectra of samp
Page 117 and 118: PERFORMANCE OF THE LOW TEMPERATURE
Page 119 and 120: BENCH UNIT DESCRIPTION Process deve
Page 121 and 122: 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
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FIGURE 1: COMPARISONS OF ILLINOIS N
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Process TABLE 1: TWO-STAGE PROCESSE
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Abstract Temperature-Staged Catalyt
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Results and Discussion Reactions in
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2. 3. 4. 5. 6. Derbyshire, F. J. an
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I LL a rJJW ., .. ;> 0 i s W 8 a 31
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Materials Feeds to the WGS-solvent
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products. Thus, coupling the WGS an
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5. R. J. Xottenstette, Sandia Natio
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ENHANCED COAL LIQUEFACTION WITH STE
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change in weight being compared to
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I I aromatic ring. The group of sig
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T,\llI.l< I ASAI,YSIS OP \\YOl)Al\:
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00 3000 2000 le00 1600 1400 1200 IO
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THE EFFECT OF REACTION CONDITIONS O
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and may ultiontely form methyl-subs
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! 5. Narain, N.K., Utz, B.R., Appel
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4 (u I t + 9 (u I 337 - Q 0
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