Liquefaction co-processing of coal shale oil at - Argonne National ...
Liquefaction co-processing of coal shale oil at - Argonne National ... Liquefaction co-processing of coal shale oil at - Argonne National ...
I COAL/RESID REACTIVITY EVALUATION The reactivities of different coal/resid combinations were evaluated. All the vacuum resids were tested with one coal (Illinois No. 6, C1) and all the coals were tested with one resid (Lloydminster. R4). The subbituminous coal (Wyodak) was tested as received (14.7 wt-% moisture content, C4.1) and also dried (1.78 wt-% moisture content, C4.2). The tests were made at the operating conditions stated above with the UOP slurry catalyst. Resid reactivity screening results are summarized in Figure 2. Coal conversions ranged from 87.9 to 92.5 wt-%. Hydrogen consumption generally decreased with increasing API gravity. The heptane insoluble and non-distillable conversions followed a similar trend. Coal reactivity screening results are summarized in Figures 3 and 4. The three bituminous and the dried subbituminous (1.78 wt-% moisture content) coals showed no particular trends. MAF coal conversion and heptane insoluble conversion for each coal were similar. The subbituminous coal as received (14.7 wt-% moisture content), gave lower coal conversion (78.3 vs 90.3 wt-% for dried Wyodak) and lower heptane insoluble conversion (64.5 vs 78.8 wt-% for dried Wyodak). CONTINUOUS BENCH-SCALE OPERATIONS The objectives of the continuous bench-scale operations are to: 1) prove the process concept, 2) direct its development toward the goals of achieving maximum coal concentration in the resid/coal feed and producing the greatest distillate yield, and 3) establish a firm experimental basis on which to evaluate a conceptual commercial facility. The early work reported here has been directed at the first and third objectives. A simplified block diagram of the pilot plant is shown in Figure 5. The slurry feed (finely ground coal, petroleum resid and catalyst) is combined with hydrogenrich recycle gas and is then preheated before it enters the bottom of the upflow reactor. The products from the reactor are then separated into a gas and oil stream at the high pressure separator. The gas stream from the high pressure separator is combined with make-up hydrogen before being recycled back to the incoming fresh feed. The oil stream from the high pressure separator is sent to a stripper where the lighter hydrocarbons are separated from the heavier fraction. The lighter hydrocarbon stream is separated further in the debutanizer into C4 minus and C4 plus products. The heavier hydrocarbon stream from the stripper is sent to a vacuum fractionator to obtain appropriate fractions. A temperature and space velocity survey was conducted processing Illinois No. 6 coal (C1.2) and a commercially fractionated Lloydminster resid (RE) with the UOP slurry catalyst. The commercially fractionated Lloydminster resid is lighter than the Lloydminster (R4) used in the autoclave studies, containing 15 vol-% more 510°C minus material. The tests were made at the operating conditions stated below. Three temperatures and three space velocities were run. 1 , > I Resid Coal Resid/Coal Ratio Pressure, psi! Temperature, C Operatinq Conditions R8, Lloydminster Vacuum Bottoms C1.2. Illinois No. 6 2 3000 Varied WHSV, G/Hr/cc Varied i 183 The effects of temperature on product distribution and conversions are shown in Table 5. The product distributions give the expected trends, an increase of lighter
fractions and a decrease of heavier fractions with increasing temperature. Coal conversion and heptane insoluble conversion exhibited an interesting trend in the higher temperature range. At the lowest temperature, 83.0 wt-% of the MAF coal was converted. Coal conversion increased to 91.8 wt-% at the mid-temperature, and then decreased slightly to 90.7 wt-% at the highest temperature. Heptane insoluble conversion behaved similarly, increasing from 72.8 wt-% at the lowest temperature to 82.2 wt-% at the mid-temperature, then decreasing to 72.5 wt-% at the highest temperature. The fact that both coal conversion and heptane insoluble conversion decreased at the highest temperature suggests that the highest temperature is too severe. resulting in thermal degradation reactions. catalytic effects predominate over thermal effects. At lower temperatures, The effects of residence time on product distribution and conversion are shown in Table 6. The product distributions show an increase of lighter fractions and a decrease of heavier fractions with longer residence time. However, coal conversion and heptane insoluble conversion show adverse responses to the longest residence time. At 1.01 WHSV (g/hr/cc reactor volume), 86.8 wt-% of the MAF coal was converted. Coal conversion increased to 91.8 wt-% at 0.78 WHSV, and then decreased slightly to 90.5 wt-% at the 0.62 WHSV. Heptane insoluble conversion behaved similarly , increasing from 75.7 wt-% at 1.01 WHSV to 82.2 wt-% at 0.78 WHSV, then decreasing significantly to 69.9 wt-% at 0.62 WHSV. Analogous to the high temperature experiment, both decreased coal conversion and decreased heptane insoluble conversion at the lowest space velocity suggest that too severe an operating condition, in this case residence time, is resulting in thermal degradation reactions. CONCLUSIONS The single-stage, slurry-catalyzed Co-processing concept was successfully demonstrated in laboratory batch experiments. The active UOP catalyst gave high coal conversion and high conversion to liquid product at relatively low temperature and, as a result, thermal degradation reactions and cracking of resid- and coal- derived liquid to light gases were minimized. The liquid hydrocarbon product is of high quality and can be efficiently utilized as a feedstock in existing refineries. The continuous bench-scale operation gave similar performance to the laboratory batch experiments, satisfying the proof-of-concept objective. In addition, data generated to date initiate a firm experimental basis on which to evaluate a conceptual commercial facility. These data show that the Co-processing process is sensitive to high severity conditions (temperature, residence time). High coal con- version and high conversion to high quality liquid product can be achieved by operating at relatively mild conditions where thermal degradation reactions are minimized. ACKNOWLEDGMENl The author expresses his thanks to Beckay J. Nelson, John G. Sikonia and Carl Lea of the Signal Research Center and Michael J. Humbach and Charles P. Luebke of UOP Inc. for their contributions to this study; and to Burtron H. Davis of the Kentucky Center for Energy Research Laboratory for the acquisition and preparation of the coal samples. This work,is supported by DOE Contract DE-AC22-84PC70002, "Coal Liquefaction Co-Processing". 1. 2. REFERENCES J. G. Gatsis. U.S. Patent 3.705.092. "Solvent Extraction of Coal by a Heavy Of 1 " (1972). s. w. Weller, "Catalysis in the Liquid Phase Hydrogenation of Coal and Tars," Ch 7 in "Catalysis," Vol 4, P. H. Emmett (ed) Reinhold. New York (1956). 184
- 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 and 30: CATALYTIC CO-PROCESSINS OF OHIO NO.
- Page 31: CATALYST COMPARISON STUDY The premi
- 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
I<br />
COAL/RESID REACTIVITY EVALUATION<br />
The reactivities <strong>of</strong> different <strong>co</strong>al/resid <strong>co</strong>mbin<strong>at</strong>ions were evalu<strong>at</strong>ed. All the<br />
vacuum resids were tested with one <strong>co</strong>al (Illinois No. 6, C1) and all the <strong>co</strong>als were<br />
tested with one resid (Lloydminster. R4). The subbituminous <strong>co</strong>al (Wyodak) was<br />
tested as received (14.7 wt-% moisture <strong>co</strong>ntent, C4.1) and also dried (1.78 wt-%<br />
moisture <strong>co</strong>ntent, C4.2). The tests were made <strong>at</strong> the oper<strong>at</strong>ing <strong>co</strong>nditions st<strong>at</strong>ed<br />
above with the UOP slurry c<strong>at</strong>alyst.<br />
Resid reactivity screening results are summarized in Figure 2. Coal <strong>co</strong>nversions<br />
ranged from 87.9 to 92.5 wt-%. Hydrogen <strong>co</strong>nsumption generally decreased<br />
with increasing API gravity. The heptane insoluble and non-distillable <strong>co</strong>nversions<br />
followed a similar trend.<br />
Coal reactivity screening results are summarized in Figures 3 and 4. The three<br />
bituminous and the dried subbituminous (1.78 wt-% moisture <strong>co</strong>ntent) <strong>co</strong>als showed no<br />
particular trends. MAF <strong>co</strong>al <strong>co</strong>nversion and heptane insoluble <strong>co</strong>nversion for each<br />
<strong>co</strong>al were similar. The subbituminous <strong>co</strong>al as received (14.7 wt-% moisture <strong>co</strong>ntent),<br />
gave lower <strong>co</strong>al <strong>co</strong>nversion (78.3 vs 90.3 wt-% for dried Wyodak) and lower heptane<br />
insoluble <strong>co</strong>nversion (64.5 vs 78.8 wt-% for dried Wyodak).<br />
CONTINUOUS BENCH-SCALE OPERATIONS<br />
The objectives <strong>of</strong> the <strong>co</strong>ntinuous bench-scale oper<strong>at</strong>ions are to: 1) prove the<br />
process <strong>co</strong>ncept, 2) direct its development toward the goals <strong>of</strong> achieving maximum<br />
<strong>co</strong>al <strong>co</strong>ncentr<strong>at</strong>ion in the resid/<strong>co</strong>al feed and producing the gre<strong>at</strong>est distill<strong>at</strong>e<br />
yield, and 3) establish a firm experimental basis on which to evalu<strong>at</strong>e a <strong>co</strong>nceptual<br />
<strong>co</strong>mmercial facility. The early work reported here has been directed <strong>at</strong> the first<br />
and third objectives.<br />
A simplified block diagram <strong>of</strong> the pilot plant is shown in Figure 5. The slurry<br />
feed (finely ground <strong>co</strong>al, petroleum resid and c<strong>at</strong>alyst) is <strong>co</strong>mbined with hydrogenrich<br />
recycle gas and is then prehe<strong>at</strong>ed before it enters the bottom <strong>of</strong> the upflow<br />
reactor. The products from the reactor are then separ<strong>at</strong>ed into a gas and <strong>oil</strong> stream<br />
<strong>at</strong> the high pressure separ<strong>at</strong>or. The gas stream from the high pressure separ<strong>at</strong>or is<br />
<strong>co</strong>mbined with make-up hydrogen before being recycled back to the in<strong>co</strong>ming fresh<br />
feed. The <strong>oil</strong> stream from the high pressure separ<strong>at</strong>or is sent to a stripper where<br />
the lighter hydrocarbons are separ<strong>at</strong>ed from the heavier fraction. The lighter<br />
hydrocarbon stream is separ<strong>at</strong>ed further in the debutanizer into C4 minus and C4 plus<br />
products. The heavier hydrocarbon stream from the stripper is sent to a vacuum<br />
fraction<strong>at</strong>or to obtain appropri<strong>at</strong>e fractions.<br />
A temper<strong>at</strong>ure and space velocity survey was <strong>co</strong>nducted <strong>processing</strong> Illinois No. 6<br />
<strong>co</strong>al (C1.2) and a <strong>co</strong>mmercially fraction<strong>at</strong>ed Lloydminster resid (RE) with the UOP<br />
slurry c<strong>at</strong>alyst. The <strong>co</strong>mmercially fraction<strong>at</strong>ed Lloydminster resid is lighter than<br />
the Lloydminster (R4) used in the autoclave studies, <strong>co</strong>ntaining 15 vol-% more 510°C<br />
minus m<strong>at</strong>erial. The tests were made <strong>at</strong> the oper<strong>at</strong>ing <strong>co</strong>nditions st<strong>at</strong>ed below.<br />
Three temper<strong>at</strong>ures and three space velocities were run.<br />
1<br />
,<br />
><br />
I<br />
Resid<br />
Coal<br />
Resid/Coal R<strong>at</strong>io<br />
Pressure, psi!<br />
Temper<strong>at</strong>ure, C<br />
Oper<strong>at</strong>inq Conditions<br />
R8, Lloydminster Vacuum Bottoms<br />
C1.2. Illinois No. 6<br />
2<br />
3000<br />
Varied<br />
WHSV, G/Hr/cc Varied<br />
i 183<br />
The effects <strong>of</strong> temper<strong>at</strong>ure on product distribution and <strong>co</strong>nversions are shown in<br />
Table 5. The product distributions give the expected trends, an increase <strong>of</strong> lighter
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