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

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that the equilibrium was unfavorable for hydrogenation of some of the high-boiling polycyclic-aromatic compounds at the run conditions. Therefore, we tried an two-step approach: (1) Hydrotreat at relatively high temperature (e.g., 750°F) to remove most of the heteroatoms. (2) Further hydrogenate at lower temperatures (e.g.,600-650°~) for further aromatics saturation. In the next test, product from the initial experiment (75O0F, 0.5 LHSV, 2300 psia H2), which contained 42 % aromatics, was hydrotreated a second time using the same catalyst. The LHSV and pressure were kept the same, but the temperature decreased to 650°F--1000F lower than previously. Due to the more favorable equilibrium at 650°F. product aromatics were reduced to 12%. The jet and diesel fractions, respectively, exceeded smoke point and cetane number specifications. Also, enough EP reduction was achieved so that less than 5% of the product boiled above the diesel range. When,the temperature was further decreased to 6OO0F, the aromatic content of the product did not decrease further, but increased to 20%. [The rate of hydrogenation was lower, although the equilibrium was even more favorable than at 65OOF.l The diesel fraction still met the cetane number specification, however. The results show that two-step hydrotreating [with the second hydrotreatment at a relatively low temperature] is an alternative to the hydrotreating/hydrocracking route for upgrading high EP syncrudes, provided diesel fuel is a desired product. CONCLUSIONS Coal liquids produced in the ITSL and CTSL processes with EPs from about 600°F to over 900°F were hydrotreated to make diesel and jet fuels, and naphthas suitable for catalytic reforming to gasoline. Specific conclusions are as follows: (1) Oils from two-stage processes were easier to upgrade than comparable boiling-range products from single-stage processes, due to lower nitrogen and oxygen contents. However, as with products from single-stage processes, relatively small increases in EPs made the oils much harder to upgrade. (2) Except for modest differences in paraffin contents, properties of finished products of given boiling ranges from both wyodak and Illinois coals, and both one- and two-stage processes studied were fairly similar, and mainly consisted of cyclic hydrocarbons. Products from Wyodak coal were somewhat more paraffinic than those from Illinois coal. (3) Product boiling ranges were different, depending upon the liquefaction process and the cut point used in that process. The single-stage processes made more naphtha than the two-stage processes at a given cut point; the two-stage processes made more middle distillate. The ITSL process made more middle distillate than the CTSL process. Diesel products from two-stage processes had higher cetane numbers at a given aromatic content than those from single-stage processes. At least in part, this was due to product boiling range differences. 289
(4) In all cases studied, the jet fuel and diesel products had high densities and, therefore, high volumetric-energy contents. (5) Wyodak CTSL light oil had a higher hydrogen content and lower heteroatom content than the other oils. These factors, plus its low EP, made it easier to upgrade than the other syncrudes studied. (6) For high EP syncrudes, an attractive upgrading route is a two-step process--hydrotreating to remove most of the heteroatoms, followed by low-temperature hydrogenation to saturate aromatics. ACKNOWLEDGMENT This work was funded by the US Department of Energy under DOE Contract DE-AC22-76ET10532. The feedstocks were provided by Hydrocarbon Research, Inc., and Lummus Crest, Inc. The analytical work was performed by the Research Services Department of Chevron Research Company. REFERENCES 1. Chevron Research Co., Refining and Upgrading of Synfuels from Coal and Oil Shales by Advanced Catalytic Processes, DOE Reports DOE/ET/10532 Series, National Technical Information Service, US Department of Commerce, Springfield, Virginia 22161. (See reference 6 for a more detailed listing of interim reports.) 2. R. S. Chillingworth, J. D. Potts, H. D.Schindler, J. M. Chen, M. Peluso, Preprints, Div. Petroleum Chem., ACS, 2 (4), Sept. 1982, pp. 859-876. 3. J. B. MacArthur, J. E. Duddy, A. S. Ambegaonkar, A. V. Moomjy, "H-Coal Liquids - Upgrading Upstream or Downstream," AIChE 1983 Spring Natl. Meeting, Houston, March 27-31, 1983. 4. J. B. McLean, A. G. Comolli, J. B. MacArthur, Preprints, Div. Petroleum Chem., ACS, 30 (3), Aug. 1985, p. 530. TAbstract only, Manuscript Available from Authors.] 5. D. J. O'Rear, R. F. Sullivan, B. E. Stangeland, ACS Symposium Series 156, Edited,by R. F. Sullivan, American Chemical Society, Washington D. C. 1981, pp. 115-144. 6. R. F. Sullivan and H. A. Frumkin, Preprints, Div. Fuel Chem., (2), April 1986, pp. 325-339. 7. R. C. Robinson, H. A. Frumkin, R. F Sullivan, Energy Progress, 3 (3). Sept. 1983, pp. 163-172. 8. R. F. Sullivan, D. J. O'Rear, 8. E. Stangeland, Preprints, Div. Petroleum Chem., ACS, 25 (3), Aug. 1980, pp. 583-607. 9. R. F. Sullivan, Preprints, Div. Petroleum Chem., ACS, 0 13), Aug. 1985, pp. 503-512. 290
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
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 and 102: Materials The catalyst was shell 32
Page 103 and 104: CONCLUSIONS Separation of a light h
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: Table VI EFFECT OF BOILING RANGE ON
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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 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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