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

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I SINGLE-STAGE SLURRY CATALYZED CO-PROCESSING John G. Gatsis Signal Research Center Inc Box 5016 Des Plaines, Illinois 60017-5016 INTRODUCTION UOP Inc. and the Signal Research Center are currently engaged in a Department of Energy (DOE) sponsored program to determine if a slurry catalyzed, single-stage process involving the simultaneous conversion of coal and petroleum resid offers the potential for improved economics. The program has been structured to accomplish the overall objectives of evaluating the technical feasibility and establishing a process data base on the Co- processing concept. Specific objectives include the establishment of overall criteria for the selection of coal type and petroleum characteristics, evaluation of process performance, and the cost estimation of a conceptual commercial facility. This paper reviews results from the first phase of the program and early results from the continuous bench-scale unit currently in operation. PROPOSED PROCESS CONCEPT UOP Inc. and the Signal Research Center began development of the resid/coal Coprocessing concept in 1970 and were issued a key patent in this area in 1972 (1). The information gained in this work plus the much longer and more extensive experience in petroleum resid upgrading and coal conversion were used to formulate a slurry catalyzed, single-stage process for the simultaneous conversion of coal and petroleum resid. This Co-processing process utilizes an active, well-dispersed catalyst and operates at relatively low temperatures. This allows high coal conversion without cracking of resid and coal to light gases, and minimizes thermal degradation reactions. FEEDSTOCK SELECTION Six vacuum resids, three bituminous coals and one subbituminous coal were selected for study. The vacuum resids were selected based on their commercial importance (availability) and to provide a wide range of chemical and physical properties. These resids were vacuum fractionated to 510°C at the 5 vol-% point so that all would have similar boiling ranges, thus eliminating any process variations due to different amounts of vacuum gas oil (VGO) in the feedstock. The chemical and physical properties are shown in Table 1. Figure 1 shows the relationship of API gravity with respect to hydrogen, C7 insolubles and carbon residue content. The contaminants (C7 insolubles and carbon residue) increase and hydrogen content decreases with decreasing API gravity. The coal samples were selected primarily because of their use as references in other studies. The properties are shown in Table 2. The Wyodak Coal as received (C4.1) has a moisture content of 14.7 wt-%. It was dried in the laboratory to a moisture content of 1.78 wt-% (C4.2). 181
CATALYST COMPARISON STUDY The premise of this work involves the concept that an active slurry catalyst will efficiently promote and effect the necessary dissolution and upgrading reactions as compared with a less active catalyst or a non-catalytic process. and thus maximize coal conversion and upgrading of the petroleum resid to produce a high quality syncrude. Disposable, iron-based slurry catalysts, whose activities have been reported as being much lower than that of other metal slurry catalysts (2). have been shown to provide beneficial catalytic effects in the upgrading of coal and coal/resid mixtures (3,4). An iron-based slurry catalyst was tested to establish a comparison with the active UOP slurry catalyst. The iron-based disposable catalyst selected was a porous iron oxide (Fe2O3) from Kerr-McGee (5). A run was also made without catalyst. Lloydminster vacuum resid (R4) and Illinois No. 6 coal (CI) were used as feedstocks. The tests were conducted in an 1800 cc rocker autoclave. The equipment and procedure have been described in previous work (6). The operating conditions are shown below: Resid/Coal Ratio 2 Pressure, psi! 3000 Temperature, C Base Residence Time, hrs 2 The iron-based catalyst was tested at twice the catalyst concentration of the UOP slurry catalyst to compensate for its lower anticipated activity with respect to the active UOP slurry catalyst. The results of this catalyst comparison study are summarized in Table 3. The addition of either catalyst resulted in dramatic increases in coal conversion and heptane insoluble conversion but had little effect on the non-distillable conversion. The coal conversion and heptane insoluble conversion without the addition of catalyst was 66.6 wt-% and 21.3 wt-%. respectively. The coal conversion and heptane insoluble conversion increased to 80.5 wt-% and 63.9 wt-% with the iron catalyst and increased further with the UOP catalyst to 92.2 wt-% and 81.3 wt-%, respectively. The non-distillable conversion (510"C+) ranged from 69.3 to 73.6 wt.% for these three tests. Although the iron oxide catalyst demonstrated some beneficial effects, its overall performance was inferior to the UOP slurry catalyst. The differences between these two catalysts becomes even more apparent when hydrogen consumption and product quality are also included as part of the evaluation. The product properties of the total liquid product for each catalyst system tested are surmnarized in Table 4. The UOP slurry catalyst has the best hydrogenation capabilities of the three Systems tested. The hydrogen consumption with the UOP slurry catalyst was 2.66 &-%. compared to 1.84 wt-% and 1.68 wt-% using no catalyst and the iron catalyst, respectively. This higher hydrogen consumption yields a liquid product with the highest API gravity, highest hydrogen content and the lowest heptane insoluble content. The higher API gravity product is important because although the product has the same boiling range as products derived from no catalyst and iron catalyst, it is less aromatic and more like petroleum fractions. Also, the lower heptane insoluble content means that the material would have a lower tendency to poison or foul conventional refinery upgrading catalysts, thus making it more economically attractive to upgrade. 182 ' I I
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 and 22: FEEDSTOCK PROPERTIES Some propertie
Page 23 and 24: CONCLUSIONS HRI's microautoclave ha
Page 25 and 26: 176
Page 27 and 28: 100. 2 8%. M = ?8. 38. .... . . . .
Page 29: CATALYTIC CO-PROCESSINS OF OHIO NO.
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 and 82:
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
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- - ITSL PAH Fraction PAH Fraction
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PROCESS DEVELOPMENT STUDIES OF TWO-
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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
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qkCqQ r! o! 0 0 0 0 0 0 0 I-UH ')I
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Materials The catalyst was shell 32
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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
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P1 #2 #3 114 115 #6 ITSL subbitumin
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temperature, time and solvent power
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TABLE 1 EXPERIMENTAL CONDITIONS AND
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la Figure 1. lH-NMR spectra of samp
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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
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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
Page 167 and 168:
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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