liquefaction pathways of bituminous subbituminous coals andtheir
liquefaction pathways of bituminous subbituminous coals andtheir liquefaction pathways of bituminous subbituminous coals andtheir
1. H* Figure 1. Quinoline HDN Reaction Network Figure 2 shows a plot of the major bond cleavage products observed at 37OOC during RuMo cat- alyzed HDN of THQ, as a function of time. In Figure 2, the quantities of propylaniline initially p m duced are not significantly higher than the propylbenzene. Furthemre, [propylcyclohexane] increases significantly with time whereas [propylbenzene] does not. Given that the amount of products produced during the course of the reaction all fall in the 0.1 to 0.8 mmol range and the starting amount of THQ is on the order of 42 mmol, the percent conversion of THQ is of the order of 1 %. Normally, the sequen- tial formation of products, as depicted in Figure 1, should not lead to the formation of significant amounts of secondary products such as propylbenzene or propylcyclohexane at conversions of 1%. Thus, these results are rather surprising. We offer two explanations for these observations, the fust is that the catalyst particles are highly porous'and that much of the catalysis occurs in the particles' interiors. In this case, the actual concentration of reactants at the catalyst surface would be much higher than it is in solution and secondary products might be expected to escape from the ~ rous body at about the same rate as primary products. Hence the relative concentrations of the two types of products seen by GC would be representative of the mixture ' rather than in solution. The second possibility is that once THQ is bound to the active catalytic site in these unsupported cat- alyst particles, it remains bound for sufficient periods of time to undergo more than one type of catalytic reaction. This would mean that the site would have a higher affinity for the reaction products and would be able to perform several different types of Catalytic operations. At this point, it is not possible to distinguish between the two possibilities; however, the surface 544
areas of the particles and the SEM micrograph^^*^ bely the possibility of a very porous catalyst particle. But tk conversions are sufficiently low that it m y be that some of this type of pomsity exists and is re- sponsible for most of the catalytic activity. Further studies will be required to differentiate between these, or other, possible explanations. 8.OE-4 5.OE-4 4.OE-4 $ 3.OE-4 3 2.OE-4 1 .OE-4 O.OE+O 4 3 0 9 12 1s Time propylcyclohexane --O- propylbenzene ---C propylanlllne -k methylanlllne Finally, the appearance of significant quantities of methylaniline, a product of C-C rather than C-N bond hydmgenolysis suggests that there are Ru rich regions on the catalyst pardcles as this product is more typical of bulk Ru catalyzed HDN of THQ.5 ACKNOWLEDGEMENTS We wish to thank the Department of Energy and the Pittsburgh Energy and Technology Center for generous support of this work through contract no. DE-FG22-90PC90313. REFERENCES 1. Hirschon, A. S.; Wilson, Jr., R. B.; Laine, R. M.; New J. Chem., 1987,U. 543-547. 2. Hirschon, A. S.; Wilson, Jt, R. B.; Laine, R. M.; in Adv. in Coal Chemistry, Theophrastus Publ, Athens 1988, p 351. 3. Hirschon, A. S.; Wilson Jr., R. B.; Laine,R. M.; J. Appl. Cat., 1987,2, 311-316. 4. bine. R. M.; Hirschon, A. S.; Wilson Jr., R. B.; U.S. Pat. No. 4,716,142 1987. 5. Hirschon, A. S. ; Laine, R. M.; J. Energy and Fuels, 1988,z. 292-295. 6. KOO, S-M.; Ryan,D. B.; andLaine, R. M.; Appl. Organornet. Chem., 1992.6, 437-448. 7. Hoppe, M. L.; Koo, S-M.; Ryan, D. B.; and Laine, R. M.; submitted to Energy and Fuels. 8. a.Satterfield, C.N.; and Cocchetto, J.F.; AICHE J., 1975,21, 1107-1111. b. Yang, S. H. and Satterfield, C.N., J. Catal. 1983,fi. 168-178. 545
- Page 19 and 20: -0.01- . 04 5 -0.03- E 6 -0.0s- c)
- Page 21 and 22: Assessment of Small Particle Iron O
- Page 23 and 24: yields are calculated by subtractin
- Page 25 and 26: conversion is greater than the corr
- Page 27 and 28: Table 3. Effect of Superfine Iron O
- Page 29 and 30: EFFECT OF A CATALYST ON THE DISSOLU
- Page 31 and 32: inherent volatility of Mo(CO), perm
- Page 33 and 34: 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: THQ at somewhat higher temperatures
- 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
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- Page 83 and 84: The effect of Corn20 preaatment on
- Page 85 and 86: Reaction Time Figure 1 - Schematic
- Page 87 and 88: DISSOLUTION OF THE ARGONNE PREMIUM
- 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
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- Page 115 and 116: of some of the thermobalance runs.
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- Page 119 and 120: Influence of Drying and Oxidation 0
areas <strong>of</strong> the particles and the SEM micrograph^^*^ bely the possibility <strong>of</strong> a very porous catalyst particle.<br />
But tk conversions are sufficiently low that it m y be that some <strong>of</strong> this type <strong>of</strong> pomsity exists and is re-<br />
sponsible for most <strong>of</strong> the catalytic activity. Further studies will be required to differentiate between<br />
these, or other, possible explanations.<br />
8.OE-4<br />
5.OE-4<br />
4.OE-4<br />
$ 3.OE-4<br />
3<br />
2.OE-4<br />
1 .OE-4<br />
O.OE+O 4<br />
3 0 9 12 1s<br />
Time<br />
propylcyclohexane<br />
--O- propylbenzene<br />
---C propylanlllne<br />
-k methylanlllne<br />
Finally, the appearance <strong>of</strong> significant quantities <strong>of</strong> methylaniline, a product <strong>of</strong> C-C rather than C-N<br />
bond hydmgenolysis suggests that there are Ru rich regions on the catalyst pardcles as this product is<br />
more typical <strong>of</strong> bulk Ru catalyzed HDN <strong>of</strong> THQ.5<br />
ACKNOWLEDGEMENTS<br />
We wish to thank the Department <strong>of</strong> Energy and the Pittsburgh Energy and Technology Center for<br />
generous support <strong>of</strong> this work through contract no. DE-FG22-90PC90313.<br />
REFERENCES<br />
1. Hirschon, A. S.; Wilson, Jr., R. B.; Laine, R. M.; New J. Chem., 1987,U. 543-547.<br />
2. Hirschon, A. S.; Wilson, Jt, R. B.; Laine, R. M.; in Adv. in Coal Chemistry, Theophrastus<br />
Publ, Athens 1988, p 351.<br />
3. Hirschon, A. S.; Wilson Jr., R. B.; Laine,R. M.; J. Appl. Cat., 1987,2, 311-316.<br />
4. bine. R. M.; Hirschon, A. S.; Wilson Jr., R. B.; U.S. Pat. No. 4,716,142 1987.<br />
5. Hirschon, A. S. ; Laine, R. M.; J. Energy and Fuels, 1988,z. 292-295.<br />
6. KOO, S-M.; Ryan,D. B.; andLaine, R. M.; Appl. Organornet. Chem., 1992.6, 437-448.<br />
7. Hoppe, M. L.; Koo, S-M.; Ryan, D. B.; and Laine, R. M.; submitted to Energy and Fuels.<br />
8. a.Satterfield, C.N.; and Cocchetto, J.F.; AICHE J., 1975,21, 1107-1111. b. Yang, S. H. and<br />
Satterfield, C.N., J. Catal. 1983,fi. 168-178.<br />
545
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