Subsequent to our post concerning the US EPA's up-to-speed issuance of guidelines for coal liquefaction industry, we wanted to send along one of the most recent artifacts we've been able to unearth from the US Department of Energy. As with seemingly all of their coal liquefaction efforts, despite the urgency and immediate importance of the issue, it is more than a decade old. But, the full information should be available, somewhere. If it is not, then someone really needs to start asking some hard questions.
Herein we present what we have so far been able to mine concerning the United States Department of Energy's project, Number AC22-91PC91056: "Molecular Catalytic Coal Liquid Conversion".
We enclose a link to the report, as well as an attached file.
Our questions and comments, as is our usual practice, and which you should be able to predict as you read the excerpt, questions and comments which we think all coal-concerned patriots should have, are appended following the excerpt:
"Quarterly Progress Report
Molecular Catalytic Coal Liquid Conversion
United States Department of Energy Grant
#DE-AC22-91PC91056
Molecular Catalytic Coal Liquid Conversion
United States Department of Energy Grant
#DE-AC22-91PC91056
Leon M. Stock - Principal Investigator
Carlos Cheng, Michael Ettinger - Research Staff
March 31, 1993
DISCLAIMER
This report was prepared as an account of work sponsored by an agency of the United States
Government. Neither the United States Government nor any agency thereof, nor any of their
employees, makes any warranty, express or implied, or assumes any legal liability or responsibility
for the accuracy, completeness, or usefulness of any information, apparatus, product, or
process disclosed, or represents that its use would not infringe privately owned rights. Reference
herein to any specific commercial product, process, or service by trade name, trademark,
manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation,
or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof.
Government. Neither the United States Government nor any agency thereof, nor any of their
employees, makes any warranty, express or implied, or assumes any legal liability or responsibility
for the accuracy, completeness, or usefulness of any information, apparatus, product, or
process disclosed, or represents that its use would not infringe privately owned rights. Reference
herein to any specific commercial product, process, or service by trade name, trademark,
manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation,
or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof.
DISTRIBUTION OF THIS DOCUMENT IS UNLIMITED
Quarterly Progress Report
Molecular Catalytic Coal Liquid Conversion
United States Department of Energy Grant
#DE-AC22-91 PC91056
#DE-AC22-91 PC91056
LeonM, Stock, Principal Investigator
Carlos Cheng
Michael Ettinger
Research Staff
Michael Ettinger
Research Staff
March 31, 1993
Molecular Catalytic Coal Liquid Conversion
I. Abstract
Last quarter, substantial progress has been made in the two general tasks advanced in our research proposal. The first task consists of the development of molecular homogeneous catalysts that can be used in the hydrogenation of coal liquids and in coal conversion processes. The second task concerns the activation of dihydrogen by basic catalysts in homogeneous reaction systems. With regards to the first task, we have prepared two organometallic rhodium (I) catalysts.
Last quarter, substantial progress has been made in the two general tasks advanced in our research proposal. The first task consists of the development of molecular homogeneous catalysts that can be used in the hydrogenation of coal liquids and in coal conversion processes. The second task concerns the activation of dihydrogen by basic catalysts in homogeneous reaction systems. With regards to the first task, we have prepared two organometallic rhodium (I) catalysts.
These are the dimer of chloro-penta-methyl-cyclo-pentadienyl-rhodium, [RhCI2(CsMes)], and the dimer of
chloro(1,5-hexadiene)rhodium. We have subsequently investigated the hydrogenation of various aromatic organic compounds using these organometallic reagents as catalysts. Results showed that both catalysts effected the hydrogenation of the aromatic portions of a wide range of organic compounds, including
aromatic hydrocarbons and aromatic compounds containing the ether group, alkyl groups, amino and carbonyl groups. However, both compounds were totally ineffective in catalyzing the hydrogenation of sulfur-containing aromatic organic compounds. Nevertheless, both rhodium catalysts successfully catalyzed the hydrogenation of naphthalene even in the presence of the coal liquids. With regards to base-activated hydrogenation of organic compounds, we have found that hydroxide and alkoxide bases are capable of activating dihydrogen, thereby leading to the hydrogenation of phenyl-substituted alkenes. Thus far, we are the first group to apply this unusual method towards the successful hydrogenation of olefins.
aromatic hydrocarbons and aromatic compounds containing the ether group, alkyl groups, amino and carbonyl groups. However, both compounds were totally ineffective in catalyzing the hydrogenation of sulfur-containing aromatic organic compounds. Nevertheless, both rhodium catalysts successfully catalyzed the hydrogenation of naphthalene even in the presence of the coal liquids. With regards to base-activated hydrogenation of organic compounds, we have found that hydroxide and alkoxide bases are capable of activating dihydrogen, thereby leading to the hydrogenation of phenyl-substituted alkenes. Thus far, we are the first group to apply this unusual method towards the successful hydrogenation of olefins.
More specifically, tetrabutylammonium hydroxide, potassium tert-butoxide and potassium phenoxide were successfully used to activate dihydrogen and induce the hydrogenation of trans-stilbene. Potassium tert-butoxide was found to be slightly more effective than the other two bases in accomplishing this chemistry.
(There is an involved dissertation regarding organometallic catalysts, which we don't include here, but which invites reading by qualified coal partisans.)
The second task will concern the activation of dihydrogen by basic catalysts in homogeneous reaction systems. This elementary concept finds clear precedenting early experimental work, in more recent fundamental gas phase research, in the demonstration that the water gas shift reaction can be catalyzed by bases, and in theoretical analyses of the chemistry. In essence, it has been established that the hydroxide ion,OH-, converts dihydrogen, He,to a hydride-equivalent reagent, [0H.H_-, that is capable of transferring
hydrogen to organic molecules under relatively mild conditions. We shall investigate whether basic catalysts ranging from hydroxide to hydrosulfide ion can accomplish the addition of dihydrogen to coal liquids and the removal of heteroatoms from them.
hydrogen to organic molecules under relatively mild conditions. We shall investigate whether basic catalysts ranging from hydroxide to hydrosulfide ion can accomplish the addition of dihydrogen to coal liquids and the removal of heteroatoms from them.
(They are confirming earlier and less clear research we have not yet cited for you, that some hydroxides, simple, well-known chemically reactive compounds related to the active ingredients in such mundane products as Drano(r), can help to facilitate coal conversion reactions in "relatively mild", i.e., lower-temperature, lower-energy, lower-cost processing "conditions".)
Observations
A. Metal-Catalyzed Hydrogenation
This phase of the project essentially consists of preparing organometallic reagents which are known or have been reported to act as homogeneous hydrogenation catalysts of aromatic hydrocarbons and studying their properties as homogeneous hydrogenation catalysts under various conditions with the ultimate objective of using these compounds to catalyze the conversion of coal liquids.
This phase of the project essentially consists of preparing organometallic reagents which are known or have been reported to act as homogeneous hydrogenation catalysts of aromatic hydrocarbons and studying their properties as homogeneous hydrogenation catalysts under various conditions with the ultimate objective of using these compounds to catalyze the conversion of coal liquids.
Furthermore, we have carried out an experiment ... to determine whether the sulfur-containing coal liquid would inhibit the hydrogenation of naphthalene (itself a coal-derived liquid) and measure the extent of inhibition. ... the results showed that 91% of the naphthalene was hydrogenated ... . to give 85% tetralin and 5% decalin. ... (and) ... this result indicate that the ... hydrogenation still proceeds to a large degree. This is a most encouraging result, since it suggests that the sulfur in coal liquid will not completely inhibit hydrogenation of the aromatic portions of the coal liquid.
(Many complex details of the chemistry of this "most encouraging result", which a qualified reader might find informative, are presented in the report. - JtM)
II. Base-Catalyzed Hydrogenation
Our second task is to investigate the chemistry of base-catalyzed hydrogenation of organic compounds with the ultimate objective of applying the chemistry behind this novel concept to the catalytic conversion of coal liquids.
It is not generally known that bases such as the hydroxide ion are capable of activating dihydrogen to form "solvated hydride" or hydride-like species which can effect hydrogenation reactions under the appropriate conditions. Research during the first half of this century has amply demonstrated the feasibility of this concept
(Again, they reiterate the effectiveness of the simple "hydroxide ion" in promoting "hydrogenation reactions"; a fact apparently "amply demonstrated" during the early 1900's. Demonstrated, but not publicized. - JtM)
Overall, the four experiments confirmed the possibilities of this kind of chemistry."
---------
In other words, these DOE researchers "confirmed the possibilities" of low-energy, catalyzed coal liquefaction, in a "Quarterly Progress Report" of research into "Molecular Catalytic Coal Liquid Conversion".
Where, is the "Full Report"? .
These researchers confirmed lower-energy coal liquefaction for the US DOE. The DOE hasn't yet, though, in turn, confirmed it to, and for, those of us who most deserve to know: