WV Coal Member Meeting 2024 1240x200 1 1

UND Liquefies Coal for USDOE

 
We've reported several times on the achievements of the University of North Dakota's Energy and Environmental Research Center in the liquefaction of coal, and their likely participation with the United States Air Force, in the proposed establishment of a coal-to-liquid conversion facility at or near the Malstrom USAF Base.
 
Herein, via the link enclosed above and the attached file, it's revealed that the University has been at work, for the USDOE, in the further development of processes to liquefy "low-rank coal", i.e., lignite, which would be lower in Btu content and higher in ash than West Virginia bituminous; but, which might compare in those respects to older accumulations of Appalachian coal mine wastes, at sites where the coal was mined specifically for eastern steel mills. Coal shipped from those mines had to be far "cleaner" than steam coal, and much carbonaceous product was separated and discarded along with incombustible waste during on-site cleaning and preparation processes.
 
So, from nearly fifteen years ago, we have:
 
"DIRECT LIQUEFACTION OF LOW-RANK COAL
 
Quarterly Technical Progress Report
 
for the period January 1 -March 31, 1995
 
Grant No. DE-FG22-94PC94050
 
Submitted to:
 
U.S. Department of Energy
Pittsburgh Energy Technology Center
PO Box 10940
Pittsburgh, PA 15236-0940
Submitted by:
 
Melanie D. Hetland
 
Energy & Environmental Research Center
University of North Dakota
PO Box 9018
Grand Forks, ND 58202-9018  
 
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.
 
April 1995
 
EERC DISCLAIMER
 
LEGAL NOTICE This research report was prepared by the Energy & Environmental Research Center (EERC), an agency of the University of North Dakota, as an account of work sponsored by U.S. Department of Energy. Because of the research nature of the work performed, neither the EERC nor any of its 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, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement or recommendation by the EERC.
 

DISCLAIMER
 
Portions of this document may be illegible in electronic image products. Images are produced from the best available original document."
 
Of course. We expect no less. But, we'll excerpt some brief portions of the report:
 

"DIRECT LIQUEFACTION OF LOW-RANK COAL
Grant No. DE-FG22-94PC94050
 

QUARTERLY TECHNICAL PROGRESS REPORT
for the period January 1 -March 31, 1995
 

EXECUTIVE SUMMARY
 
A multistep direct liquefaction process specifically aimed at low-rank coals (LRCs) has been developed at the Energy & Environmental Research Center (EERC). The process consists of a preconversion treatment to prepare the coal for solubilization, solubilization of the coal in the solvent, and polishing using a phenolic solvent or solvent blend to complete solubilization of the remaining material. The product of these three steps can then be upgraded during a traditional hydrogenation step.
 
This project will address two research questions necessary for the further development and scaleup of this process: 1) determination of the recyclability of the solvent used during solubilization and 2) determination of the minimum severity required for effective hydrotreatment of the liquid product. The project will be performed as two tasks,the first consisting of ten recycle tests and the second consisting of twelve hydrotreatment tests performed at various
conditions.
 
Several activities were performed during this quarter.
 
The composite solvent was redistilled to verify that the light material could be quantitatively recovered from the heavier vehicle solvent fraction.
 
Additional heavy fraction was prepared from coal derived hydrogenated anthracene oil (HA061) for use as the vehicle solvent during the Task 1tests.
 
(Note: We have previously documented the effective use of coal-derived oils, i.e., "anthracene", as coal solvents and hydrogenating agents.)
 
A simulated product slurry was prepared and distilled to verify that the water, cresylic acid (POW, and HA061 light fraction could be separated from the coal andlor coal-derived liquids.
 
1.0 INTRODUCTION
Direct liquefaction research at the Energy & Environmental Research Center (EERC) has, for a number of years, concentrated on developing a direct liquefaction process specifically for low-rank coals (LRCs) through the use of hydrogen donating solvents and solvents similar to coal derived liquids, the water/gas shift reaction, and lower-severity reaction conditions. The underlying assumption of all of the research was that advantage could be taken of the reactivity and specific qualities of LRCs to produce a tetrahydrofuran (THF)-soluble material that might be easier to upgrade than the soluble residuum produced during direct liquefaction of high-rank coals. A multistep approach was taken to produce the THF-soluble material, consisting of 1) preconversion treatment to prepare the coal for solubilization, 2) solubilization of the coal in the solvent, and 3) polishing to complete solubilization of the remaining material. The product of these three steps can then be upgraded during a traditional hydrogenation step.
 
(Did, or does, anyone in Appalachian Coal Country know there was/is such a thing as "a traditional hydrogenation step" in the preparation of coal liquids? Is anything, about any of this, so established and commonplace as to be considered "traditional"?)
 
The results of the EERC’s research indicated that additional studies to more fully develop this process were justified. Two areas were targeted for further research: 1)determination of the recyclability of the solvent used during solubilization and 2) determination of the minimum severity required for hydrotreatment of the liquid product. This project addresses these two areas.
 
(Further work is at least "justified". But, when are we, like the Germans and Japanese during WWII, and like the South Africans for the last several decades, going to stop talking about justifications, and just start doing it? - JtM)
 
4.0 FUTUREOBJECTIVES
The Task 1and Task 2 tests will be performed, the products analyzed, and the data reduced and interpreted. Quality assurance checks will be performed as outlined in the project quality assurance plan. Preparation of the final technical report will begin during the next quarter."
 
Well that "next quarter", during which they were to begin "Preparation of the final technical report", would have been April-June, 1995. Fourteen and a half years ago.

Monsanto Patents CO2 Recycling

 
 
We earlier documented, through reports of Japanese research, that Carbon Dioxide can be captured and used as a raw material in the manufacture of useful plastics.
 
We also documented that the United States Department of Defense, through proxies, holds US Patents on the technology to recycle Carbon Dioxide into liquid fuels.
 
Herein, we document that a US chemical company, Monsanto, was issued, fifteen years ago, a United States patent on the use of Carbon Dioxide to manufacture urethane, much as described in the reports of Japanese research we posted to you.
 
Excerpt as follows: 

"Preparation of urethane from polyamine and carbon dioxide

Patent number: 5371183
Filing date: Nov 16, 1992
Issue date: Dec 6, 1994

The present invention provides a process for preparing urethanes and carbonates from an amine or an alcohol, carbon dioxide and a hydrocarbyl halide. The amine or alcohol is reacted with carbon dioxide in a suitable solvent system and in the presence of an amidine or guanidine base, to form the... (urethane).
Inventors: William D. McGhee, Dennis P. Riley
Assignee: Monsanto Company"
 
Our US Government has officially known for fifteen years that Carbon Dioxide can be productively recycled into a very useful, and carbon-sequestering, plastic.
 
That, in addition to the USDOD patents, held by proxies, on the recycling of CO2 into more fuels.
 
Yet, a decade and a half after issuance of the patent enclosed herein, our coal industries are still threatened with extortions like Cap-and-Trade, and Geologic Sequestration.

Japan Liquefies Coal, Recycles Carbon with WVU CoalTL Tech

 
There are a number of what we think to be interesting things going on in this Japanese research into coal liquefaction.
 
It confirms a conjecture we earlier presented, and should help, we think, to pave the way for the full utilization of coal in liquefaction processes; and, point the way to one route of Carbon Dioxide recycling.
 
Excuse the following, over-long, prologue, but:
 
We have documented that some, especially "indiect", coal liquefaction technologies leave behind a residual material that still has a significant carbon content. We suggested that such residual carbon could itself be recovered and liquefied, made available for hydrogenation and refining, through direct, hydrogen-donor solvent technologies, such as WVU's West Virginia Process for direct coal liquefaction. 
 
We did, in fact, document that coal liquefaction residue from FMC Corporation's New Jersey, "COED", coal conversion facility was sent to Spain for further liquefaction processing.
 
We cited reports from several sources, especially from some in the United Kingdom, that rubber waste from used auto tires could, like coal and coal indirect liquefaction residues, be converted into liquid hydrocarbons appropriate for refining; and, in at least one other report, that used tires actually improved coal liquefaction processes, presumably by supplying additional Hydrogen.
 
Herein, Japanese researchers confirm that used tires can enhance the liquefaction, the recycling, of indirect coal liquefaction residues produced by their own, "NEDOL", coal liquefaction technology, about which we have also earlier reported.
 
And, interestingly, they describe the use of tetralin, the hydrogen donor solvent we believe specified by WVU in the West Virginia direct coal liquefaction Process, as has other research we've brought to your attention, as being effective in the liquefaction of tire rubber; and, in, as suggested, the extraction of remaining carbon from indirect coal liquefaction residues. 
 
The excerpt:

"Effects of reaction conditions on the hydrogenolysis reaction of tire and coal liquefaction residue.

Authors: Onda Daigoro, Oba Toshiaki, Koyano Koji (Nihon Univ., Coll. of Sci. and Technol.)
 
Journal: Nippon Enerugi Gakkai Sekitan Kagaku Kaigi Happyo Ronbunshu; Vol.37th; Pages 245-248 (2000)
 
Abstract: The NEDOL process produced coal liquefaction residue(CLR) in about 30% yield. The amount of waste tire is increasing every year. In this study, the hydrogenolysis reaction of CLR(1t/d PSU) with pulverized waste tire was carried out by using tetralin. Compared with the result from each reaction of CLR or tire alone, the synergistic effects to upgrading, such as the increase of the yield of volatile products and the decrease of n-hexane insoluble-acetone soluble materials, were observed."
 
In other words, as we interpret this, combining residue from a primary indirect coal liquefaction process with pulverized waste auto tires, in a secondary direct liquefaction process using tetralin as the Hydrogen donor solvent, resulted in "synergistic effects", with an "increase of the yield of" desired "volatile products" and a decrease  in the yield of, seemingly undesired, "hexane insoluble" products. 
 
Note, again, that using waste tires in such liquefaction processes would, to the extent that the tires might be composed of natural latex compounds, represent an indirect route of atmospheric carbon dioxide recycling through botanical agents.

Pittsburgh Company Coal Conversion Technology

 
The length of this dispatch might be warranted, if anyone is truly interested in following up on the genuine potentials presented by coal, as a source of raw material from which we can synthesize both liquid fuels and industrial organic chemicals.
 
We have, in earlier posts, mentioned the Pittsburgh company, Koppers, as having coal gasification technology that can be employed in conversion processes targeted on the production of liquid fuels.
 
In fact, in an earlier report, we disclosed that coal liquefaction residues from FMC's New Jersey COED plant had been sent to Spain for further processing to extract even more carbon values for further conversion.
 
According to other sources, that Spanish facility used a Koppers coal gasification unit to process those coal liquefaction residues. 
 
Moreover, in multiple reports, we documented that coke oven by-products, coal tars, could be harvested and converted into liquid fuels, and commercially valuable organic chemicals.
 
Coal tars, their extraction and use, are a specialty of Koppers, as the following excerpt from the link above reveals: 

"The corporation is divided into two divisions: Carbon and Chemicals, and Railroad and Utility. The company specialises in manufacturing carbon chemicals from coal tar. The five main chemicals that are produced are coal pitch for steel and aluminum production, carbon black for rubber vulcanization, creosote for wood treatment, and naphthalene and phthalic anhydride for plastics and polyester."

Without citation, we submit that it has been documented that much of China's planned, and extensive, coal liquefaction industry is to be targeted on the production, specifically, of plastics manufacturing raw materials, including, and especially, napthalene. 

Koppers, in fact, has a long history of manufacturing "substitute" organic chemical products from coal, as in the following excerpts:

"In 1943, Koppers, at the US Government's behest, built a factory in Kobuta, Pennsylvania ... to manufacture styrene-butadiene monomer ... used to make a form of synthetic rubber" from coal.

"In 1951, ...  the company built a plant to manufacture the chemical monomer ethylbenzene, using as raw materials ethylene from the nearby Gulf Oil refinery, and benzene, which was a byproduct of the company's coke ovens ... ." Further processing resulted in "styrene monomer" which was "then polymerized to make expandable polystyrene."

"Koppers operates facilities in the United States, United Kingdom, Denmark, Australia, China, South Africa. Koppers sources coal tar from around the world for further processing by distillation into carbon chemicals. The Company owns its own coke oven battery in Monessen, Pennsylvania. The Monessen facility operates 57 ovens with a combined annual capacity of over 360,000 tons of coke. The company further operates coke ovens in Tangshan, People's Republic of China, and has co-located facilities near the operations of major steel makers."

Koppers' expertise in coal extraction technologies was recognized quite some time ago by both the United States Government, and some major petroleum producers, when Koppers was selected to participate in, and provide expertise for, a little-known US Government-sponsored coal-to-liquid conversion project; one which we some time ago, in a brief dispatch, documented for you as having been established at Allentown, Pennsylvania. It was another of the "Solvent Refined Coal" developments, and did involve petroleum industry participants, as documented in: 

 
"Title: SRC-1 Quarterly technical report, April-June 1980; (Though, strangely, reported as being published in January of 1980.)
 
Report Numbers: OSTI ID: 6753958; DOE/OR/03054-T2; DOE Contract Number: AC05-780R03054
 
Research Organization: International Coal Refining Co., Allentown, PA ("International" because Shell Oil was a participant, with Koppers.)
 
Abstract: The SRC-1 quarterly report has chapters on: an evaluation of current technologies for deashing coal liquids; domestic vendors of thick-wall pressure vessels; a comparative evaluation of GKT, Texaco and Shell-Koppers gasification processes (GKT is a modification of Koppers-Totzek and is recommended for reasons given); disposal or gasification of residues; evaluation of one or two slurry feed tanks; evaluation of one or two critical solvent deashing trains; analysis of causes of corrosion in the fractionating tower (chlorides and phenols); identifying and planning for pollution control in the demonstration plant; and characterizing waste center and monitoring its treatment. 236 Pages."
 
Note the size of this quarterly report.
 
In any case, that government-sponsored research likely helped in the development of the Koppers-Totzek coal gasification technology, which has many applications for the production of synthetic liquid fuels and organic chemicals, as evidenced by the following:
 
 
"ECONOMICS OF THE KOPPERS K-T GASIFICATION PROCESS FOR SYNTHETIC GAS AND CHEMICAL MANUFACTURE
 
John F. Kamody and J. Frank Cannon
 
Koppers Company, Inc.
Engineering and Construction Group
Pittsburgh, PA 15219
 
The commercially proven Koppers K-T gasification process is employed for the gasification of coal and other carbonaceous fuels to produce a carbon monoxide and hydrogen rich gas (i.e., "syngas").
 
Since 1952 a total of 39 gasifiers have been installed at 13 locations in the Eastern Hemisphere. (what about the Western Hemisphere?) An additional plant at Talcher, India, is scheduled for start-up (in) 1978. The latest commissioned plant, in ... South Africa, produces ... Methanol ... (and) Ammonia."
 
And, very significant:
 
"Unlike natural gas, hydrogen to carbon monoxide ratios of 1:1 are readily obtainable without the need for (added) hydrogen or importation of carbon dioxide. This feature can make the K-T (coal) process more practically suited than natural gas for ... methanol production, or Fischer-Tropsch technology."
 
Fischer-Tropsch technology, as you know, is one way to make liquid fuels from coal.
 
And, if you produce methanol, you can, as has been more than thoroughly documented, convert it into gasoline, as per the ExxonMobil "MTG"(r) technology..

"An additional major advantage to the process is its ability to handle a variety of feed stocks, including all ranks of coal"
 
And other carbonaceous, and carbon-recycling materials, one supposes. 
 
Koppers' work at Allentown, PA, did lead to a commercial coal conversion technology, in addition to the Koppers-Totzek process: The "Shell-Koppers Coal Gasification Process", presumably in support of Sasol, in South Africa. As evidenced, following:
 
 
Title: Development of the Shell-Koppers coal gasification process
 
Authors: Vogt, E.V.; van der Burgt, M.J.
 
Affiliation: Shell Internationale Petroleum, The Hague, Netherlands
 
Publication: Royal Society Philosophical Transactions, Series A, vol. 300, no. 1453, Mar. 20, 1981
 
Abstract: The Shell-Koppers process for the gasification of coal under pressure is based on the principles of entrained-bed technology. It is characterized by practically complete gasification of virtually all solid fuels, production of a clean gas without by-products, high throughput, high thermal efficiency, efficient heat recovery, and environmental acceptability. The gas produced is 93 to 98 vol % hydrogen and carbon monoxide and is suitable for the manufacture of hydrogen or reducing gas, and, with further processing, substitute natural gas. It can also be used for the synthesis of ammonia, methanol, and liquid hydrocarbons. The process can be applied as an integral part of a combined-cycle power station featuring both gas and steam turbines, which will yield electricity generation at 42 to 45% efficiency for a wide range of feed coals. A 150 t/day gasifier has been put into operation successfully at Harburg, Germany, achieving a conversion of 99% for hard coal, and units of a capacity up to 2500 t/day are planned for the end of the 1980s."
 
Note: "Gas produced" from coal "is suitable for the manufacture of ... substitute natural gas" and "can also be used for the synthesis of ... methanol, and liquid hydrocarbons."

U Pitt and Syngas

 
We've previously cited the University of Pittsburgh's Wender, and others, on the subject of carbon conversion technology.
 
Herein is presented more information from them on the topic of "C-1" technologies that can convert basic sources of carbon, such as coal, into more versatile hydrocarbons, such as the liquid fuels we've all come to know and love.
 
As with so much US research we've been able to mine for you, this piece is more than two decades old.
 
The excerpt:
 
"Title: Synthesis gas as a source of fuels and chemicals: C-1 chemistry
 
Author: I. Wender; Dept. of Chemical and Petroleum Engineering, Univ. of Pittsburgh, Pittsburgh, PA
 
Date: January, 1986; OSTI: 6991112; Journal: Annual Review of Energy; Volume 11; Pages: 295-314
 
Abstract:
 
This chapter is concerned with the present and future uses of synthesis gas as a source of fuels and chemicals. Synthesis gas, a mixture of hydrogen and carbon monoxide in various ratios, is important both as a fuel and as a feedstock for chemical synthesis. Fully developed processes are available for producing it from natural gas, petroleum, petroleum derivatives, and coal. Synthesis gas, in fact, can be made from almost any organic material, including biomass and organic wastes, and increasingly diverse raw materials may find use in the future. The composition of the raw synthesis gas produced can vary widely, depending on the process technology and the quality of the raw materials (especially their hydrogen-to-carbon ratios and their reactivities)."
 
We will close by repeating a few of Dr. Wender's words: "Synthesis gas ... is important both as a fuel and as a feedstock for chemical synthesis. Fully developed processes are available for producing it from ... coal" or "any organic material, including" carbon-recycling "biomass and organic wastes".
 
And, once we have the syngas, as everyone should by now know, it can be converted, via a selection of technologies, into liquid petroleum substitutes.
 
The University of Pittsburgh knew all of that more than twenty years ago.
 
How come the rest of us in the US Coal Country environs around Pittsburgh don't seem to know it, yet?
 
And, why aren't we using any of those "Fully developed processes" to convert our abundant domestic, local, coal into the liquid fuels and chemical manufacturing materials we all, as a nation, need?