WV Coal Member Meeting 2024 1240x200 1 1

Coal Liquefaction in Nitrogen Compounds

Coal liquefaction in nitrogen compounds
Francis J. Derbyshire, George A. Odoerfer and D. Duayne Whitehurst

Mobil Oil Corporation, Mobil Research and Development Corporation, Central Research Division, Princeton, NJ 08540, USA

July, 1983.


Abstract

Model compound studies have shown that 1,2,3,4-tetrahydroquinoline is an exceptionally good coal solvent. In the pure compound, subbituminous coal conversion to THF-soluble products approaches 100% under relatively mild reaction conditions. The effectiveness of tetrahydroquinoline for coal conversion appears to be related to its concentration relative to coal. The unique behaviour of tetrahydroquinoline is ascribed to its being a highly active H-donor; the fact that it is regenerable under reaction conditions by the reaction of hydrogen and quinoline; and that its polarity allows penetration of the coal structure and aids in dispersion of the dissolved coal. It has been found that, during reaction with coal, tetrahydroquinoline and other nitrogen compounds undergo extensive condensation reactions which result in an increase in the nitrogen content of the high boiling and non-distillable liquefaction products.

(Note: "1,2,3,4-tetrahydroquinoline" is also know as "Tetralin", and is the hydrogen-donor solvent specified by WVU in their "West Virginia Process" for coal liiquefaction.) 


Temperature-Staged Catalytic Coal Liquefaction

Temperature-staged catalytic coal liquefaction 

Frank Derbyshire, Alan Davis, Mike Epstein and Peter Stansberry

Fuel Science Program, Coal Research Section, College of Earth and Mineral Sciences, The Pennsylvania State University, University Park, PA 16802, USA


March 1986.
 

Abstract

An investigation has been made of the liquefaction of a bituminous and a subbituminous coal under conditions where reaction is conducted in successive stages of increasing temperature and in the presence of a dispersed sulphided Mo catalyst. This sequence has been found to lead not only to high coal conversion but to greatly increase the selectivity of the liquefied products to oils at the expense of asphaltenes. These gains are made with marginal increases in the production of light hydrocarbon gases. Although no systematic attempt has yet been made to determine the specific influence of reaction parameters upon liquefaction behaviour, preliminary results show that there is substantial potential for further improvement through the suitable choice of solvent and reaction conditions in the two stages. The reasons for the effectiveness of temperature staged liquefaction are discussed in terms of the balance between hydrogenation and condensation reactions. Examination of the liquefaction residues by optical microscopy has provided strong supporting evidence to show that the staged reaction sequence favours hydrogenative processes. Moreover, the microscopic examination has proved to be a powerful diagnostic technique, showing, for example, that the first stage temperature should be lower for the subbituminous than the bituminous coal, and providing insight into the processes of catalysed liquefaction. 


Two-Stage Liquefaction of a Subbituminous Coal

Frank J. Derbyshire, P. Varghese and D.Duayne Whitehurst

Mobil Research and Development Corporation, Central Research Division, PO Box 1025, Princeton, NJ 08540, USA

Abstract

The two-stage conversion of a subbituminous coal has been investigated using an autoclave reactor system. The overall performance of the reaction is found to be determined by the effectiveness of the first-stage operation and by the method of sequencing of the stages. The initial thermal products can undergo condensation reactions which render them unresponsive to subsequent catalytic conversion and which increase the light gas yield. This can occur during the first stage reaction, if there is limited capacity for free-radical stabilization, and upon storage and/or thermal cycling between stages. The latter effects are circumvented by operating the two stages in immediate sequence. Condensation is also reduced by increasing the solvent quality and the solvent:coal ratio. The presence of a catalyst during thermal decomposition of coal can greatly improve conversion and product stability even at short reaction time and can reduce constraints on solvent quality. The more feasible approaches to improving first-stage operation appear to be in controlling the solvent composition and in employing hydrogenation catalysts.

Question - WVU & Dr John W Zondlo


 
We earlier cited some of John Zondlo's work, we think "Stiller, A.H., J.-P. Wann, D. Tian, J.W. Zondlo and D.B. Dadyburjor, "Co-Processing of Agricultural and Biomass Waste with Coal," Fuel Proc. Technol., in press (1996)" to be one of the sunbmissions. Is anyone/everyone comfortable sending his contact particulars and the info about his work to the journalists we've been copying in? None of them have expressed rabid interest, but, if they actually had someone to talk to, it might help. Does James Dean have similar curriculum vitae, as below? 
"Dr. Zondlo's research program is centered around the investigation of fundamental phenomena underlying coal utilization and processing. Much of the work is process oriented and touches on the areas of reaction engineering, solution chemistry and the use of catalysts in synthetic fuels production. Currently, a class of novel solvents is being studied for use in the extraction and separation of clean solid and liquid carbonaceous materials from coal at mild conditions. In addition, novel coal liquefaction catalysts are being developed and tested in a variety of liquefaction reactor configurations. Finally the use of coal as a precursor for the manufacture of value-added carbon products is being investigated.
 
Liu, Z., J.W. Zondlo, and D.B. Dadyburjor, "Coal/Tire Co-Liquefaction Using an Iron Sulfide Catalyst Impregnated In-situ in the Coal," Energy and Fuels, 9, 673-679 (1995).

Liu, Z., J.W. Zondlo and D.B. Dadyburjor, "Tire Liquefaction and Its Effect in Coal Liquefaction," Energy and Fuels, 8, 607-612 (1994).

Selected Publications

Khandare, P., J.W. Zondlo and A.S. Pavlovic, "The Measurement of the Glass Transition Temperature of Mesophase Pitch Using a Thermomechanical

Stiller, A.H., J.-P. Wann, D. Tian, J.W. Zondlo and D.B. Dadyburjor, "Co-Processing of Agricultural and Biomass Waste with Coal," Fuel Proc. Technol., in press (1996).

Liu, Z., J. Yang, J.W. Zondlo, A.H. Stiller, and D.B. Dadyburjor, "In-situ Impregnated Iron-Based Catalysts for Coal Liquefaction," Fuel, 75, 51-57 (1996).

Liu, Z., J.W. Zondlo, and D.B. Dadyburjor, "Coal/Tire Co-Liquefaction Using an Iron Sulfide Catalyst Impregnated In-situ in the Coal," Energy and Fuels, 9, 673-679 (1995).

Liu, Z., J.W. Zondlo and D.B. Dadyburjor, "Tire Liquefaction and Its Effect in Coal Liquefaction," Energy and Fuels, 8, 607-612 (1994).

Seehra, M., A. Pavlovic, V. Babu, J.W. Zondlo, P.G. Stansberry and A.H. Stiller, "Measurements and Control of Anisotropy in Ten Coal-Based Graphites," Carbon, 32(3), 431-435 (1994).

Dadyburjor, D.B., W.R. Stewart, A.H. Stiller, C.D. Stinespring, J.-P. Wann, and J.W. Zondlo, "Disproportionated Ferric Sulfide Catalysts for Coal Liquefaction," Energy and Fuels, 8, 19-24 (1994).

Stansberry, P.G., J.P. Wann, W.R. Stewart, J. Yang, J.W. Zondlo, A.H. Stiller and D.B. Dadyburjor, "Evaluation of a Novel Mixed Pyrite/Pyrrhotite

Monazam, E.R., J.W. Zondlo and E.K. Johnson, "A Comparison of Model Predictions and Experimental Data for the Gasification of Coke in a CrossflowGasifier," Fuel Science Technology Intl., 11, No. 2, 293-310 (1993).

Renganathan, K. and J.W. Zondlo, "Non-destructive Extraction Mechanism of Bituminous Coals Using N-methyl-2-Pyrrolidone," Fuel Science Technology Intl., 11, No. 5-6, 677-695 (1993).

Gerstner, J.A. and J.W. Zondlo, "Gasification Kinetics of Residual Coal Produced From Solvent Extraction with N-methyl pyrrolidone," Fuel Science Technology Intl., 10, No. 3, 335-346 (1992).

Monazam, E.R., E.K. Johnson and J.W. Zondlo, "Modeling and Simulating of a Crossflow Coal Gasifier," Fuel Science Technology Intl., 10, No. 1, 51-73 (1992). Device," Carbon, 34(5), 663-669 (1996). Catalyst for Coal Liquefaction," Fuel, 72, No. 6, 793-796 (1993).

CO2 Recycling Via CoalTL

 
We submit the attached links and following excerpted info in case anyone is interested in further investigating the potentials for combining CO2-recycling, bio-derived Ethanol and/or cellulose-derived Methanol, in "direct" coal conversion processes, such as WVU's, combined with the primary Hydrogen-donor solvents specified in those processes.
 
We understand that a few of our recent posts could cause some confusion, based on the fact that there are multiple ways, i.e. direct and indirect, in which coal can be converted into liquid fuels; and, in the ways through which botanical products, including, by extension, ethanol and methanol (wood alcohol), can be added to a coal conversion process for beneficial effect.
 
With that, herein is more info. An additional link, and brief comment, follows below. And, there is an additional, United States, patent application "out there" to which this International Patent Application refers. 

"Patent application title: Synthesizing Hydrocarbons of Coal with Ethanol

Publication No.: WO/2007/011700        International Application No.: PCT/US2006/027314
Publication Date: 01/25/07       International Filing Date: 07/14/06
Applicant/Inventor: Mills, Anthony (US)
 
Title: SYNTHESIZING HYDROCARBONS OF COAL WITH ETHANOL
 
Abstract: A novel fuel for the gasoline-powered internal combustion engine and an additive for the diesel combustion engine is provided by producing an Ethanol/Coal synthesization that approaches the BTU content of Gasohol. In one implementation the synthesizing process is performed by extracting hydrocarbons from the coal using a release agent and synthesizing the extracted coal hydrocarbons with an ethyl alcohol product to produce a fuel suitable for use in an internal combustion engine."
 
 
We have seen a number of references elsewhere to "release agents", as in "extracting hydrocarbons from the coal using a release agent", above, with no really definitive explanation of what they might be, or what the term might mean. "Tetralin", correctly or incorrectly, has been named as one, though most references identify Tetralin as an agent of coal dissolution that supplies Hydrogen ions as part of the hydrogenation and liquefaction process.
 
And, very similar to the tetralin/alcohol synergy info earlier transmitted, we have:
 
 
"Coal characterization for liquefaction in tetralin and alcohols 

P.N. Kuznetsov, G.I. Sukhova, J. Bimer, P.D. Salbut, E.D. Korniyets, N.A. Belskaya and N.M. Ivanchenko

Institute of Chemistry and Chemical Technology, 42 K. Marx St, Krasnoyarsk 660049, USSR

Institute of Organic Chemistry, 44 Kasprzaka, Warszawa 01–224, Poland

Abstract

Kansk-Achinsk lignite hydrogenation in tetralin, isopropanol, ethanol and methanol was studied. Tetralin was the most active solvent. Synergetical effects were observed when the mixture of tetralin and alcohols was used for liquefaction." 

Note again the now almost-trite application of "synergy" to describe the effects of mixing tetralin and alcohols in direct coal liquefaction processes. We've no idea if WVU's direct "WV" coal liquefaction "Process", which does, we believe, involve the use of tetralin, also calls for the synergistic inclusion of   CO2-recycling alcohols derived from botanical sources, such as ethanol, as fermented from various plants, or methanol, as can be derived from botanical cellulose.

But, certainly, the heavily-documented usefulness of alcohols derived from botanical sources provides elements of both Carbon recycling and sustainability to a system of liquid fuel manufacturing based on coal.