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

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EXPERIMENTAL Wyodak coal was pretreated and treated with steam in a semi-Row micro reactor at controlled conditions to exclude oxygen. The apparatus is depicted in Figure 1. The main components are a Milton Roy metering pump (29 to 290cm3/hr) which provides a continuous and constant Row of distilled deoxygenated water to the reator, a Tecam fluidized sand bath (model SBS-4) controlled with a Leeds and Northrup controller (Electromax Ill), a Helicoid pressure gauge (0 to 3000 PSIG), an autoclave micro metering valve and a Picro reactor equipped with a sheathed thermocouple (see Figure 2). The feed material was an unweathered subbituminous Wyodak coal provided by EPRI in a water slurry kept in a sealed air-tight barrel (#4171). Table 1 shows the elemental analysis of samples taken from this barrel. Samples A and B were taken from the top and middle of the barrel and were suction dried for use. These were the main feed material. About a 50 gm sampled of this material was removed from the barrel and vacuum dried; a sample of this material is repoted as sample C. A tew reactions were carried out with this material. The suction dried coal was prepared in a Buchner filter, by applying suction to it tor about one hour. The top portion of the material was removed from the filter and thoroughly mixed to insure a homogeneous sample for reaction. The moisture content of this material (z 30 wt %) was determined by weighing a sample before and after further drying in a vacuum oven at 45 O c for 6 hours. Duplicate samples were used for moisture determinations. Suction dried Wyodak coal is paste-like, and is messy to bandle. A free-Rowing coal powder was obtained for reaction experiments by drying the coal in vacuum under mild heating. The vacuum dried coal wan prepared by suction drying in a Buchner funnel over nitrogen; the material was then transferred in a jar 611ed with nitrogen, to a vacuum oven and dried for 72 hours at 45 O c. The experimental reaction procedure for vacuum dried coal was similar to suction dried coal except that the separate moisture determination of the dried coal was no longer necessary. To prepare for reaction the oven dried micro reactor (see Figure 2) was weighed and then filled with about 4 gm ot wet suction dried coal or 3 gm of vacuum dried coal and reweighed for an accurate determination of the quantity of material charged to the reactor. The charged reactor was fitted into the apparatns upon connecting tubings and fittings. The system was purged of air by Rushing with nitrogen. Enough water was pumped from the buret into the reactor to raise the pressure to SO pia, about 10 to nCm3 being required. The reactor was lowered into the sand bath, the pressure adjusted to 750 psia with the aid of the micro metering valve, as water was pumped into the system at 0.4cm3/min. The steam generated in the heating coil passed through the reactor, was condensed, and collected in an Erlen- meyer Bask. At the termination of an experiment the reactor WBB removed trom the aand bath, and placed in a vacuum oven over night at 45 O c to remove any water. The reactor was then wekhed, the contents were removed and placed in a predried and weighed thimble. The reactor was then reweighed, the 322
change in weight being compared to the weight gain of the thimble. The coal in the thimble was extracted with toluene for 4 to 6 hours in a Soxhlet apparatus. The thimble was dried over night in a vacuum oven and reweighed to detemined the amount of coal extracted. On selected runs the effluent collected in the Erlenmeyer Bask was extracted with chloroform and sent to analysis. The only time the coal sample was exposed to oxygen of the air was during suction drying at ambient temperature. Oxyged was carefully excluded from the reaction system. Feed water to the reactor was deoxygenated by blowing it with nitrogen. >From the time of steam pretreatment the reactor remained tightly closed and completely isolated from air until the reactor was cooled down after steam treatment. The only coal that was heated before reaction was that which was vacuum dried at 45 c. The suction dried coal was never heated. EXPERIMENTAL RESULTS Table 2 shows the conversion of Wyodak coal upon pretreatment and treatment with steam at 750 pia. Treatment and pretreatment (if used) steps each lasted 30 minutes. Conversion expresses the fraction of coal that was extracted by the steam from the reactor plus the fraction that was extracted by toluene from the Soxhlet apparatus. The toluene extraction was small, ranging from 0% to less than 3% of the total reported conversion. Toluene extraction was incorporated in our experimental procedure in order to put our experimental results on the same basis with those of other investigators (3,4,5,6) who wash their coal residue with toluene. With suction dried coal, when not pretreated, treatment with steam at 200 c gives a practically zero (2.2%) conversion. Raising the treatment temperature to 400 * c raisea the conversion to 30.5%. Pretreatment with steam at 200 c further raises the conversion to 38.5%. Raising the pretreatment temperature to 240 ' c raises the conversion to 40.3%. This is the highest conversion observed in this work, for, upon raking the pretreatment temperature to 320 e c conersion is lowered to 33.8%. Raising the treatment temperature to 430 c further lowers the Conversion to 34.2%. The conversion of vacuum dried coal is reported in the second part of Table 2, and is generally lower than the corresponding results for suction dried coal. Even the mild heating at 45 O c during vacuum drying made the coal more refractory. Comparison of the results obtained with the two diRerent coal samples convinced us to stop using vacuum dried coal. All other experiments reported here used suction dried coal. The conversions reported in Table 2 were obtained with 750 psia steam for both the pretreatment snd tnatment. The eUect of steam pressure at the treatment stage was investigated, the results are reported in Table 3. Holding the pretreatment pressure constant at 750 psi, an increase in treatment preasure from 750 tO 260 psia, produced a slight reduction in the observed conversion. Higher pressure apparently increm the rate of retrograde reactions. This eRect more than compensates for any increase 323
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
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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
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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
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 and 138: Table VI EFFECT OF BOILING RANGE ON
Page 139 and 140: (4) In all cases studied, the jet f
Page 141 and 142: 292
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: ENHANCED COAL LIQUEFACTION WITH STE
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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