liquefaction pathways of bituminous subbituminous coals andtheir

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Bimetallic RulMo Catalyst Particles for HDN of Tetrahydroquinoline Daniel B. Ryan, Thomas Hinklin, Gregory Reuss, S.-M. Koot and Richard M. Laine, Conhibution from the Departments of Materials Science and Engineering, and Chemistry, University of Michigan, Ann Arbor, MI 48109-2136, *Depart. of Chemistq and Eng., Hanyang University Seoul, Korea KEY WORDS: Unsupported RuMo Bimetallic Catalysts, Tetrahydroquinoline Hydrodenitmgenation, Heteropolyanion Catalyst Recursors ABSTRACT Ethanol solutions of the hetempolyanion H3PMo1204.xH20, (Mo-HPA) mixed with RuC13 were decomposed, at 180°C in the presence of CS2 and H2 to form small multimetallic catalyst particles. Revious efforts have demonstrated the synergistic effect of these catalyst systems for Quinoline hydrogenation to THQ and alkylation of THQ by ethanol. The current study extends these efforts to the HDN of THQ in hexadecane. , I ’ NIRODUCTION We have previously shown that alumina supported RuMo and RuCoMo bi- and himetallic catalysts provide catalytic activities and product selectivities during quinoline (Q) and teaahydroquinoline (THQ hydrodenimgenation ON) that are not normally observed with alumina supported, M’Mo (M’ = Co, Ni) or single metal Mo or Ru catalysts.’-’ The RuMo combination of metals appears to offer synergistic behavior during Q and THQ HDN. In particular, the catalysts are sulfur tolerant, even showing enhanced activities in the presence of sulfur compounds. Their activities are 5 to 10 times higher than corresponding M’Mo catalysts for similar weight loadings on identical supports. Moreover, their selectivity towards the formation of propylbenzene vs. propylcyclohexane during Q or THQ HDN is much higher (1:3 product ratios at temperatures of 350°C and H2 pressures of 400-600 psig at RT). In an effort to completely delineate this synergistic behavior, we have examined the catalytic activity of RuMo catalysts with Q and THQ under a variety of conditions. Furthermore, we have examined the feasibility of preparing these heterogeneous bimetallic catalysts directly from soluble precursors based on ethanolic solutions of molybdenum hetempolyanion, H3PMo1204 @lo-HPA) and RuC13.xH20 (Ru-C1). We find that 1:9 Ru:Mo atomic ratio solutions consisting of 1.0 ml(5.7~10‘~ M, 5.7~10.~ mmol) of RuC13.x~0 in EtOH with 4.0 ml of l.l~lO-~ M in Mo-HPA (4.38~10-~ mmol) in EtOH, when heated with 5.0 ml(42 mmol) Q or THQ and 591 of CS2 for 3 h at 175-uw)oC decompose uniformly to give 0.3-1.5 pm dia. RuMo catalyst particles (surface areas typically of 5-9 m2/g)6s7 These bimetallic particles appear to be more catalytically active for Q hydrogenation to THQ than similar particles generated either from Mo-HPA or Ru-CI under identical conditions? Furthermore, efforts to promote HDN of 542
THQ at somewhat higher temperatures in EtOH solutions leads to the Nethylation of THQ rather than HDN.6 Again, the RuMo catalyst is much more effective for N-ethylation than either of the metals alone. N-ethylation was also observed when THQ HDN was attempted in acetonitrile solutions of RuMo. We have now determined that it is possible to conduct THQ HDN to the exclusion of extraneous reactions through the use of hexadecane as solvent. We describe here preliminary efforts to study this reaction. EXPERIMENTAL HDN catalysis studies were conducted using hexadecane as solvent and using 1:9 RuMo catalyst particles generated under conditions identical to the Q hydmgenation reactions, at 175°C. but in the ab sence of 4.' Particle surface. areas were 5-6 m2/g. Studies were done with two 250 mg batches of catalyst which were mixed to obtain a uniform catalyst Product analyses for all the kinetic studies were performed on a temperature programmed Hewlett- Packad 5890A reporting GC equipped with FID using a 12 m x 0.53 nun x 2.65 pm capillary column packed with 100 9% dimethyl polysiloxane gum. The column heating schedule was initiated with a hold at 35'C (2 min) followed by ramping at 7'Umin to 250'C. The eluting gas mixture was %/He. GC-MS studies were performed using an HF' 5890 Series Il GC, an HP 5970 mass spectrometer, and the HP 5940 MS Chemstation. The capillary column used for product separation was a 12 m x 0.12 mm x 0.33 film thickness HP-5 (crosslinked 5% phenyl methyl silicone) capillary column. The temperature for the analysis was held at 50'C for 5 min, then ramped at 4'Umin to 275'C. The eluting gas used was H2/He. THO HDN Kinetic Runs Typically, 18-20 mg of catalyst are added to a solution of 5.0 ml(42.3 mol) of THQ mixed with 5.0 ml of hexadecane and 50 pl of decane as internal standard in a quartz lined, Parr General Purpose Bomb reactor with a 34 ml internal volume. The reaction solution is then pressurized to 400 psig with N2 at RT and depressurized. The process is repeated and then 400 psig with H2 at RT is added and the reaction is heated, with magnetic stimng, to the desired temperature, e.g 370°C for the studies shown below. At the appropriate times (typically 3,6,9,12 and 15 h) the reactor is cooled in flowing water, depressurized and a sample is taken for GC analysis. The reactions are run to less than 5% conversion so that the initial rates of product formation correspond essentially to zero d er in reactant concentration. RESULTS AND DISCUSSION Figure 1 shows the standard reaction network for Q HDN.8 Ropylcyclohexene may arise both from hydrogenation of propylaniline and from deamination of aminopropylcyclohexane, presumed to be an intermediate in DHQ HDN. Ropylaniline and DHQ are presumed to derive directly from catalytic reactions of THQ, and propylbenzene and propylcyclohexane are presumed to arise from the catalytic reactions of propylaniline and DHQ respectively; although propylcyclohexane could also derive from propylbenzene. 543
Page 1 and 2:
LIQUEFACTION PATHWAYS OF BITUMINOUS
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the conversion of A+P and O+G with
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Asphaltcncs PrCasphaltenCS Cwr%, da
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NEW DIRECTIONS TO PRECONVERSION PRO
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ecause of incorporation of the coal
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should be considered more. The step
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17 18 Run no. 0 cys I ToS-CyS TS-To
Page 15 and 16:
INTRODUCTION Effects of Thermal and
Page 17 and 18: apid decline in modulus. The loss m
Page 19 and 20: -0.01- . 04 5 -0.03- E 6 -0.0s- c)
Page 21 and 22: Assessment of Small Particle Iron O
Page 23 and 24: yields are calculated by subtractin
Page 25 and 26: conversion is greater than the corr
Page 27 and 28: Table 3. Effect of Superfine Iron O
Page 29 and 30: EFFECT OF A CATALYST ON THE DISSOLU
Page 31 and 32: inherent volatility of Mo(CO), perm
Page 33 and 34: Analysis of the quantity and compos
Page 35 and 36: $ EO .- 0 m L 0 c 0 0 > 40 300 350
Page 37 and 38: 0 0 0 0 0.000 0.005 0.010 0.015 0.0
Page 39 and 40: of these studies indicate that cont
Page 41 and 42: Different levels of adsorption occu
Page 43 and 44: Nominal 2 Table 1. Concentration of
Page 45 and 46: - iF m 1.6 1.4 1.2 - - - 1- 0 0.8 -
Page 47 and 48: RESULTS AND DISCUSSION Swelling of
Page 49 and 50: . . % . . 9 'HF 0 0 0 *. . 0 . . 0
Page 51 and 52: 1.50 KQ 1.00 0.50 I / ' 02 525 I 1
Page 53 and 54: hydrogen atoms. The hydrogen atoms
Page 55 and 56: D to generate more D atoms. It is r
Page 57 and 58: 12. a. Poutsma, M. L.; Dyer, C. W.
Page 59 and 60: Figure 3. Minimum Steps to Explin D
Page 61 and 62: Apoaratus and Procedure Microflow R
Page 63 and 64: Model ComDound Test Figure 5 shows
Page 65 and 66: Figure 1. High resolution gas chrom
Page 67: Figure 5. Product distribution for
Page 71 and 72: areas of the particles and the SEM
Page 73 and 74: Experimental Catalyst Precursors an
Page 75 and 76: impregnating solvent. Table 3 shows
Page 77 and 78: of MoCo-TC2 at the level of 0.5 wt%
Page 79 and 80: Table 4. Effect of Temperature Prog
Page 81 and 82: In the past, chemical treatments in
Page 83 and 84: The effect of Corn20 preaatment on
Page 85 and 86: Reaction Time Figure 1 - Schematic
Page 87 and 88: DISSOLUTION OF THE ARGONNE PREMIUM
Page 89 and 90: A much more def~tive trend is seen
Page 91 and 92: EFFECT OF CHLOROBENZENE TREATMENT O
Page 93 and 94: same conditions and an extraction t
Page 95 and 96: ACKNOWLEDGEMENT The authors thank t
Page 97 and 98: THE STRUCTURAL &=RATION OF HUMINlTE
Page 99 and 100: to be originally derived from demet
Page 101 and 102: 145 30 I --/---Jh I , , I I , 250 2
Page 103 and 104: THE EFFECTS OF MOISTURE AND CATIONS
Page 105 and 106: 1 for the Zap lignite. These result
Page 107 and 108: content of the samples ion-exchange
Page 109 and 110: Table 1. F'yrolysis Results of Vacu
Page 111 and 112: 585 I
Page 113 and 114: EFFECT OF TEMPERATURE, SAMPLE SI2E
Page 115 and 116: of some of the thermobalance runs.
Page 117 and 118: 2. The mechanism of drying is a uni
Page 119 and 120:
Influence of Drying and Oxidation 0
Page 121 and 122:
"c gives W conversion mpared to the
Page 123 and 124:
Table 1. Products dismbutions (dmmf
Page 125 and 126:
- 50 45 40 E 35 2 30 E T) 25 ap 20
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Influence of Drying and Oxidation o
Page 129 and 130:
FTIR . . of the L m To investigate
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CONCLUSIONS The characexizntion of
Page 133 and 134:
A b S 0 r b a n C e A b s 0 r b a n
Page 135 and 136:
An NMR Investigation of the Effd of
Page 137 and 138:
for determining the area of the pea
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of the ronl roniponcnte nnd (2) the
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2w 180 160 9 140 120 P loo f 80 P O
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25 I 20 ' + 0 Drying lime, hours Fi
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substructure have been identified a
Page 147 and 148:
Pyridine extraction showed that 60
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Figure 1. Reflected white-light pho
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Table 3. Pyridine Extraction Sample
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A bang-bang control strategy was us
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increased from 120°C to 135”C, r
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* wt% based on the amount of naphth
Page 159 and 160:
Use of Biocatalysts for the Solubil
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Results Enzyme Modification with Di
Page 163 and 164:
Conclusions Reducing enzymes can be
Page 165 and 166:
Dynamics of the Extract Molecular-W
Page 167 and 168:
where yi = (x-xi !/pi. The zero mom
Page 169 and 170:
satisfactory agreement between theo
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0.8 0.6 0.4 0.2 “E \ bo Y, - 1 0
Page 173 and 174:
The Use of Solid State C-13 NMR Spe
Page 175 and 176:
differences lie in the fact that th
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I- z W 0 K W n PROTONATED AROMATIC
Page 179 and 180:
ZAP WIO SIDE CHAINS IN PYRIDINE EXT
Page 181 and 182:
ORGAFlIC VOLATILE MATER AND ITS SUL
Page 183 and 184:
(Figure 1). They indicated that the
Page 185 and 186:
Table 3. Elemental analysis of arom
Page 187:
1- 700'C Figure 3. GClFID chromatog
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