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

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CHEMICAL AND TOXICOLOGIC CHARACTERIZATION OF CO-PROCESSlh% AND TWO-STAGE DIRECT COAL LIQUEFAcIlON MATERIALS Cherylyn W. Wright, Dorothy L. Stewart, D. Dennis Mahlum, Edward K. Chess, and Bary W. Wilson Pacific Northwest Laboratory P. 0. Box 999 Richland, WA 99352 Research and development of advanced coal liquefaction technology is being supported by the U.S. Department of Energy (DOE) as a means of utilizing domestic supplies of coal to produce petroleum- substitute fuels. As a component of this effort, the U.S. DOE has supported the chemical analyses v d toxicological evaluations of coal conversion products and internal process materials to assess the potenhal health effects and industrial hygiene concerns associated with coal liquefaction technology. Recent advances in coal liquefaction have included two-stage direct coal liquefaction processes and petroleum residkoa1 co-processing technology. Two-stage coal liquefaction processes are generally comprised of a first-stage thermal or liquefaction reactor followed by a second-stage hydrogenation step. Petroleum resids and coal are simultaneously converted to liquefaction products in co-processing technology. The purpose of this paper is to report the preliminary results of the chemical analysis and toxicological testing of a coal liquefaction co-processing sample set, and to compare. these results to those obtained from two-stage coal liquefaction materials. SAMPLES Samples for comparative chemical analysis and toxicological evaluation were provided from the proprietary UOP, Inc. co-processing technology (Des Plaines, Illinois) and the integrated, non-integrated, reconfigured integrated, and close-coupled reconfigured integrated two-stage coal liquefaction processes (ITSL, NTSL, RITSL, and CCRITSL respectively) from the Wilsonville Advanced Coal Liquefaction Research and Development Facility (Wilsonville, Alabama) operated by Catalytic, Inc. A summary is contained in Table 1 of the co-processing samples received from UOP, Inc. and the two-stage coal liquefaction materials analyzed for comparative purposes. Since the samples provided were from pilot plant or bench-scale advanced coal liquefaction origins, they may not necessarily be representative of materials produced on a commercial basis. A description of the proprietary UOP, Inc. catalyzed, slurry, single-stage coal liquefaction co- processing technology has been given by Gatsis, et al. (1). ITSL and NTSL processes have been described by Later (2). For a brief overview of the RlTSL and CCRlTSL, see Gough et a1 . (3). EXPERIMENTAL Samples were chemically characterized by chemical class fractionation, gas chromatography, gas chromatography-mass spectrometry, and low-voltage probe-inlet mass spectrometry. Toxicological activity was measured using the standard histidine reversion microbial mutagenicity test and an initiatiodpromotion assay for mouse skin tumorigenesis. A brief description of these methods follow. . . -Class F~aXxmtm Samples were fractionated according to the method described by Later er a1 . (4) and Later and Lee (5) by sequential elution of standardized alumina (1.5% water, Later er al., 6) with 20 ml hexane, 50 ml 233
Table 1. Samples Analyzed PNLNumber Process Description 5 1396-005 51396-004 51396-001 5 1396-003 51396-002 5226-059 5226-022 50378-100 50378-101 50378-139 UOP UOP UOP UOP UOP lTSL NTSL RITSL RlTSL CCRITSL Lloydminster Peholeum Resid. Nominal boiling point (bp) >840"F, including non-distillables, no solids. Illinois No. 6 Coal and Lloydminster Pemleum Resid Slurry Feed. Nominal bp >840"F, including solids and non-distillables. Liquid Process Solvent (LPS). Nominal bp >212'F, including solids and non-distillables. Vacuum Fractionator Overhead Product. Nominal bp -212-910'F. Vacuum Fractionator Bottoms Product. Nominal bp >910'F, including solids and non-distillables. Hydrotreater (HTR) Distillation Column Bottoms. Nominal bp -450- 850'F. Run #242. HTRDistillation Column Bottoms. Nominal bp -450450°F. Run #241. HTR Heavy Distillate Product. Nominal bp >500'F, including resids and ash. Run #247. HTR Heavy Distillate Product. Nominal bp >500'F, less resids and ash. Run #247. HTR Heavy Distillate Product. Nominal bp >500T. Run #249. benzene, 70 ml ch1oroform:ethanol (99:1), and 50 ml methanol to produce aliphatic hydrocarbon (AH), polycyclic aromatic hydrccarbon (PAH), nitrogen-containing polycyclic aromatic compound WAC), and hydroxy-substituted PAH (hydroxy-PAH) fractions, respectively. The weight percent contribution of each fraction was determined gravimemcally after solvent removal by rotoevaporation at 40°C and drying under a stream of nitrogen. Bas Chroma- Selected fractions were analyzed by gas chromatography using a Hewlett-Packard (HP) 5880A gas chromatograph equipped with a 30-m x 0.25-mm-ID fused silica capillary column coated with 0.25-pm film thickness DB-5 (J & W Scientific). The oven was temperature-programmed to 280'C at 4'Clmin after 2 minutes isothermal at 50°C with a 5 minute isothermal period at the upper temperature limit. Splitless injection was used with hydrogen as carrier gas at 100 cm/sec linear velocity. The injection port and flame ionization detector were operated at 275 and 300'C, respectively. Fractions were analyzed at 5.0 mglml dilutions with 2-chlomanthracene added as an internal standard at a fmal concentration of 25 ng/@ Gas ChromatograDhvlMasstmmehv CGCMs1 GCMS analyses were performed on an HP-5982A quadrupole mass spectrometer interfaced to an HP-5710 gas chromatograph equipped with a 15-m x 0.25-mm-ID DB-5 fused silica capillary column (J & W Scientific). Gas chromatographic conditions were similar to those described above, except the oven was temperature-programmed at 8 Clmin. The MS was operated in the electron impact mode at 70 eV, and scan rates were typically 100 atomic mass units (amu)/sec. Low-Volm Probe-- Smhometrv A VG ZAB 2-F double-focusing MS operated in the electrom impact mode using ionizing electron energies of 10-12 eV was used for the LVMS analyses. Each sample (10 to 20 pg) was loaded into a glass capillary tube, which was then inserted into the source affixed to the end of a direct insertion probe. The probe was heated in a linear fashion from ambient to 250-280°C while the MS scanned repeatedly throughout the desorption period. The MS was operated with an accelerating voltage of 6OOO or 7000 V, a magnet scan rate of 2 to 3 seclmass decade, a source temperature of 250'C, and a dynamic resolving power (as determined by the VG 2035 data system) of 1:2OOO. The intensities of each mass across the entire profile were summed, generating an average spectrum that was representative of the entire sample. 234
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.
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
Page 77 and 78: Coprocessing Schemes The coprocessi
Page 79 and 80: processing 25,000 and 150,000 bbl/d
Page 81: FIGURE 1 I DISTRIBUTION OF REFINERI
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 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
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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
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Comparative Economics of Two-Stage
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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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