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

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program does not represent the "best" choice based on reactivities, but was cho- sen based on cannercia1 considerattons. OHIO COAL/COLD LAKE ASB CO-PROCESSING Figure 6 shows the reactivity curves for a 50/50 blend of Ohio coal and Cold Lake ASB. The drop off in 975'F+ conversion at 20 STTU may be indicative of some regressive reaction due to poor solvent quality, as this is the highest temperature point (825OF) in the grid. The STTU axis has been extended to include a point at a typical bench unit operating severity. It i s notable that there was no problem in achieving high (90% plus) coal conversion to TW solubles. This was true of all the pairs studied, indicating that the inherently poor hydrogen donor properties of the petroleum oils can be oveccme by catalytic, ebul lated-bed co-processing. Figure 7 shows the effect of coal to oil ratio on conversions in a low severity test (10 STTU). As expected, the THF conversion increases as the coal con- centration increases, since a higher percentage of the solvent is then coal- derived as well. The 975'F+ conversion response is far less explainable. The individual feedstock points at 0 and loo$ are connected, to represent expected conversions based on strict linear averaging. At coal concentrations up to 502, conversions near or above this line occur, indicating a positive synergy. Surprisingly, at coal concentrations of 67-758, a large negative interaction occurs, and 975OF+ conversions are actually lower than those for coal alone. Each of these points was found to be reproducible. The most likely explanation for this phenomenon is that the presence of the petroleum oils sufficiently reduces the solvent quality in this range to cause a large drop in the conversion of the coal residua. At the lower coal concentrations. this effect is offset by the improved conversions of the petroleum residua. Interestingly, this effect shows itself only in the 97S°F+ conversions and not in the THF conversions. It should be noted here that coal/oil ratio studies with other feedstock pairs do not show this same negative behavior (at least not to this extent), but in all cases the response is non-linear. Since this trend was interesting and unexpected, it was decided to repeat the coal/oil ratio studies at a higher severity, typical of bench unit process conditions. This was done to coincide with the single-stage bench mn. which pro- vided comparative results in the single-stage, integrated bench unit at 33, 50 and 67% coal. These results are shown in Figure 8. Note that the cmplex ratio response curve for 975'F+ conversion has been reproduced, although the extent of the negative deviations at 67-75% coal are reduced. The bench unit data, at 33 and 50% coal, provide excellent agreement with the microautoclave data. The bench data at 67% coal do show some negative effect, althought not as pronounced as in the microautoclave. One key difference is that each bench data point represents several days of continuous, integrated operation with solvent quality equilibration. while microautoclave solvents are artificially cmposited. It should also be noted that the tie points at 0 and 1OG% coal were not detemined on the bench unit, so that the extent of positive/negative synergy may not be directly comparable. The 50% coal case has been shown to be economically pre- ferred t several severities at least in part due to synergistic reactivity effects 39) 173
CONCLUSIONS HRI's microautoclave has been shown to be an effective tool for comparing reac- tivjties of coals, oils, and combinations for catalytic coal/oil co-processing. Specific improvements in experimental and analytical procedures were implemented to expand the utility of the microautoclave from coal liquefaction into oil and co-processing. Data generated on the Ohio coal/Cold Lake ASB combination led to some unexpected results, which were later confirmed by continuous bench unit studies. ACKNOWLEDGEMENTS HRI wishes to acknowledge the program sponsors and their representatives who have contributed to the technical content of this work. Some of the feedstock analytical data presented were generated by the Alberta Research Council. REFERENCES 1. 2. 3. 4. 5. 6. 7. 8. 9. U. S. Patent 4,054,504. "Coal/Oil Co-Processing of Canadian Feedstocks" J. B. MacArthur, F. Boehm. A. Liron, R. H. Shannon. Proceedings: Tenth Annual EPRI Contractors' Conference on Clean Liquid and Solid Fuels, October, 1985. Evaluation of Process Parameters for Combined Processing of Coal with Heavy Crudes and Residua", C. U. Curtis, et al. Ind. Eng. Chem. Process Des. Oev., 1985, 24, 1259-1266. "Use of Non-Coal Derived Heavy Solvents in Direct Coal Liquefaction" R. L. Miller. Proceedings: Tenth Annual EPRI Contractors' Conference on Clean Liquid and Solid Fuels, October, 1985. "Lumus Co-Processing", M. Green. OOE's (PETC) Direct Liquefaction Contractors' Conference. Pittsburgh, November 19, 1985 "Coal Liquefaction Co-Processing". J. Gatsis, et al. DOE'S (PETC) Direct Liquefaction Contractors' Conference, Pittsburgh, November 19, 1985 "The Chevron Co-Refining Process", J. Shinn. et al. Proceedings of 9th Annual EPRI Contractors' Conference on Clean and Solid Fuels. March 1984. "Co-Processing of Canadian Lignites and Bitumen", S. Fouda, et al. AIChE National Meeting, March 1985. "HRI's Coal/Oil Co-Processing Program - Phase I", J. E. Ouddy. Presented at EPRI's 11th Annual Conference on Clean Liquid and Solid Fuels, May 1986. 174
Page 1 and 2: ABSTRACT LIQUEFACTION CO-PROCESSING
Page 3 and 4: eaction temperature, 1000-1500 psig
Page 5 and 6: 6. 7. 8. 9. 10. 11. 12. 13. 14. 15
Page 7 and 8: I 0" 100- I I I WyO-3 P 3: 1500 psi
Page 9 and 10: 11.3 A-6 yJ 600 OF, 1500 psig CO, 3
Page 11 and 12: Experimental UDqradinq and Cooroces
Page 13 and 14: catalytic to the thermal hydrogenat
Page 15 and 16: the reaction with oil production re
Page 17 and 18: TET did not promote the production
Page 19 and 20: MICROAUTOCLAVE DESCRIPTION AND PROC
Page 21: FEEDSTOCK PROPERTIES Some propertie
Page 25 and 26: 176
Page 27 and 28: 100. 2 8%. M = ?8. 38. .... . . . .
Page 29 and 30: CATALYTIC CO-PROCESSINS OF OHIO NO.
Page 31 and 32: CATALYST COMPARISON STUDY The premi
Page 33 and 34: fractions and a decrease of heavier
Page 35 and 36: TABLE 2 Coal Analyses I1 1 i noi s
Page 37 and 38: Temperature WHSV, G/hr/cc TABLE 6 C
Page 39 and 40: z FIGURE 3 COAL REACTIVITY SCREENIN
Page 41 and 42: COPROCESSING USING HzS AS A PROMOTE
Page 43 and 44: - 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
Page 49 and 50: 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
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Coprocessing Schemes The coprocessi
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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
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the coal itself. The chemical compo
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- - 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
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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
Page 99 and 100:
qkCqQ r! o! 0 0 0 0 0 0 0 I-UH ')I
Page 101 and 102:
Materials The catalyst was shell 32
Page 103 and 104:
CONCLUSIONS Separation of a light h
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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
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temperature, time and solvent power
Page 113 and 114:
TABLE 1 EXPERIMENTAL CONDITIONS AND
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la Figure 1. lH-NMR spectra of samp
Page 117 and 118:
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
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Process Identification LV% Of AS- R
Page 133 and 134:
Table I11 HYDROTREATING TESTS WITH
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Table IV HYDROTREATING TO 0.2 PPM N
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Table VI EFFECT OF BOILING RANGE ON
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(4) In all cases studied, the jet f
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292
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INTEGRATED TWO-STAGE LIQUEFACTION:
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are over-riding features in its fav
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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
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
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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
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T,\llI.l< I ASAI,YSIS OP \\YOl)Al\:
Page 179 and 180:
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
Page 185 and 186:
! 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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