WV Coal Member Meeting 2024 1240x200 1 1

United Kingdom Liquefies Coal

 
We earlier documented that our WWII British Allies were, during the war, like our German and Japanese foes at the time, converting coal into some of the liquid fuels needed by their military.
 
British Scientists are continuing to refine and develop their coal-to-liquid processes, just like researchers in the United States. And, they are using, in their work, a coal found in the US which seems to have become a standard for CTL experimentation: "Illinois No. 6". It is a specification we have seen in several other research citations, from other places.
 
The technically dense Excerpt, with comment following :
 
"Title: Reductive alkylation of Illinois No. 6 coal in liquid ammonia
 
Author: Handy, C.I., Stock, L.M.
 
Date: August 01, 1982
 
Journal: Fuel; (United Kingdom); Journal Volume: 61:8 
 
Abstract: The reductive alkylation of Illinois No. 6 coal was investigated using alkali metals and alkyl halides in liquid ammonia. Potassium is the most effective reducing agent and butyl iodide is the most effective alkylating agent for the preparation of coal alkylate that is soluble in tetrahydrofuran. The overall yield of soluble product is often improved through the reaction of the tetrahydrofuran-insoluble portion of the initial reaction products with an alkylating agent in the presence of tetrabutylammonium hydroxide. The infrared spectra of these materials suggest that the phase transfer agent catalyses the esterification of residual carboxylic acid functions. The intermolecular interactions between such acid groups and acceptor groups markedly restrict the solubility of the coal alkylate. The gel permeation chromatograms of the soluble reaction products are essentially featureless with only modest maxima at short and long elution volumes. The proton and carbon nuclear magnetic resonance spectra of the reductive methylation products, prepared using methyl-/sup 13/C iodide, suggest that carbon alkylation exceeds oxygen alkylation and that the alkylation of phenolic groups is the dominant O-alkylation reaction. The spectra also suggest that fewer ethers are cleaved in the reaction in liquid ammonia than under the conditions of Sternberg reaction. (32 refs.)"
 
Note: We are not technically competent to explain the process of "alkylation". However, other, easily-accessible web-based references, explain that coal can be "alkylated" with well-understood comparative ease, and that such alkylated coal compounds, once produced, dissolve readily in a selection of common organic solvents, which makes subsequent refining into useful liquid fuels and chemicals a relatively straightforward process.

Texaco Liquefies Coal with Coal By-Product

 

Following through on our assertions that the by-products of coal processing, specifically coal tars, can be beneficial additives for a coal-to-liquid fuel processor of appropriate design; and, that Big Oil knows all about the fact that coal can be efficiently converted into liquid petroleum substitutes, we present the enclosed report on liquefying coal, using a coal oil product, from Texaco.
 
As follows:
 
"Coal liquefaction using a hydrogenated creosote oil solvent: H-atom transfer from hydrogen donor components in the solvent  

Erv J. Kuhlmann, Dick Y. Jung, Richard P. Guptill, Charles A. Dyke and Hyung K. Zang

Texaco Research Center, PO Box 509, Beacon, NY 12508, USA

Abstract

The presence of hydroaromatic, hydrogen donor components in a coal-derived solvent is one of the more important factors in the successful operation of a non-catalytic coal liquefaction process. Various hydrogen donor species present in a hydrogenated creosote oil have been identified. Their rate of disappearance under conditions that are consistent with a short residence time coal liquefaction process has been used to rank the reactivities of the various hydrogen donors. 1,2,3,10b-Tetrahydrofluoranthene was found to be an exceptional donor while 4,5-dihydropyrene, the hexahydropyrenes and 9,10-dihydrophenanthrene were found to be quite active. Sym.-octahydrophenanthrene and 2a,3,4,5-tetrahydroacenaphthene exhibited moderate activity. Tetralin and the four methyltetralin isomers were found to be unreactive under the coal liquefaction conditions employed."

Japan Refines Coal Liquid

We submit these coal-to-liquid research selections, from Japan, only to support, and to illustrate the validity, of our thesis that coal-to-liquid conversion technologies are well-understood in many places throughout the world, and are undergoing continuous technical refinement and efficiency improvement.
 
We've edited the excerpts from the enclosed links to simplify, in as much as might be possible, the very technical jargon. What is presented should, again, just serve as added confirmation that coal can be converted into the liquid fuels and chemical raw materials we need. The question of why our abundant coal isn't yet being so utilized is one that needs answered.
 
The excerpts, with brief comment appended:
 
  
"Selective nuclear hydrogenation of naphthalene, anthracene and coal-derived oil over Ru supported on mixed oxide 
 
Takeshi Kotanigawa, Mitsuyoshi Yamamoto and Tadashi Yoshida

Hokkaido National Industrial Research Institute, AIST, MITI Higashi-tsukisamu, Toyohira-ku, Sapporo 062, Japan


April 1997
 

Abstract:

The main objective of this paper is to investigate the possible ways to produce high-quality products for transportation fuels from heavy distillates. For this purpose (various weight percents of Ruthenium on Manganese, Zinc and Nickel Oxides) were used as catalysts for selective hydrogenation of napthalene, anthracene and Canadian Battle River coal-derived oil. The catalysts exhibited (various levels of activity). It was concluded that Ruthenium on non-acidic support showed the best performance.
 
 
 

Behavior of Hydrogen Transfer over Carbon-Supported Nickel Catalyst in Upgrading of Coal-Derived Liquid.

BINTANG B(Hniri)   ZHANG Z-G(Hniri)   NAGAISHI H(Hniri)   YOSHIDA T(Hniri)
 
Nippon Kagakkai Hokkaido Shibu Kenkyu Happyokai Koen Yoshishu
 
Abstract
The focus of this study is to investigate the behavior of hydrogen transfer over active carbon and carbon-supported nickel catalysts in the hydrotreating of coal-derived oil. In this work, the effects of donor solvent and hydrogen gas on the hydrotreating of model compounds or coal oil were examined. (author abst.)"
 
 
 
Catalysts for Upgrading Coal-Derived Oils
 
Yoshimura, T. Sato, H. Shimada, N. Matsubayashi, A. Nishijima, T. Kameoka, H. Yanase, M. Watanabe, K. Masuda, Y. Kanda, and K. Ohsuka
J. Natl. Inst. Materials and Chem. Res., Vol.3, No.2, p.145, 1995 

Abstract: Coal-derived oils were hydrotreated in two-stage catalytic processes or in single stage co-refining catalytic processes to produce high-quality oils. The former processes were much more flexible to control the quality of the final products such as gasoline and/or kerosene, depending on the reaction mode/severity of each state. In hydro-treating neat and low sulfur coal-derived oils, we developed a new type of (Nickel-Tungsten-Aluminum Oxide)  hydro-treating catalyst for the first stage use, which catalyst had higher hydrogenation and "hydrodenitrogenation" activities and better activity maintenance than the conventional (Nickel-Molybdenum-Aluminum Oxide) catalysts. A new type of  zeolite hydro-cracking catalyst, which showed high activity to convert (high temperature distillate) fraction with minimal gas make, was also developed for the second stage usage.In the latter co-refining process, where coal-derived oils were mixed with the proper fraction of petroleum oils and hydro-processed to get high-quality kerosene and/or diesel oils, (Ruthenium-Nickel-Molybdenum-Aluminum Oxide) catalysts were superior to (Nickel-Molybdenum-Aluminum Oxide) and (Nickel-Tungsten- Aluminum Oxide) catalysts. Spent Nickel-Tungsten and Nickel-Molybdenum catalysts were successfully cured by the oxidative regeneration under the low partial pressure of oxygen in the oxidizing gas and low oxidation temperature conditions."

First of all, the "heavy distillates" in the first abstract are intended to imply coal-derived oils. "Naphthalene" and "anthracene" are both constituents of crude coal "tar" or coal "oil", in the more traditional sense of those phrases.

Note, in the final abstract, mention of "processes (that) were (are) much more flexible to control the quality of the final products such as gasoline and/or kerosene"; and,.  the "high activity" of a zeolite catalyst "to convert" products from "coal-derived oils" into "high-quality kerosene and/or diesel".

Zeolite catalysts, as we hope you'll recall, are at the heart of Exxon-Mobil's "MTG"(r) process which converts methanol to gasoline; methanol that's posited to be made from coal.

Again, the technical language might seem confusing, but the import is quite clear: We know how to convert coal into liquid hydrocarbon fuels. 

 

Oklahoma Upgrades Coal Liquids

 
We earlier submitted a collection of three research reports, from Japan, which revealed detailed investigations into the upgrading of hydrocarbon liquids derived from coal, into products more akin to the liquid fuels were all familiar with; specifically, kerosene and gasoline.
 
The same sort of research has been underway much closer to home, but still not in Coal Country, though just as quietly, as the enclosed report, from Oklahoma State University, bears witness.
 
Comment follows:
 
"Catalysts for Upgrading Coal-Derived Liquids. Quarterly report, October-December, 1980.
 
Author: Crynes, B.L.
 
Report Number: DOE/ET/14876-T1; DOE Contract Number: AC22-79ET14876
 
Research Organization: Oklahoma State University, School of Chemical Engineering, Stillwater, OK
 
Abstract:
 
A linear relationship represents the hydrogenation activity decay of catalysts used in four experimental runs reported previously. The weight percent hydrogen in the reactor product oils plotted against oil-catalyst contact time for experimental runs ZBB, ZBC, ZBD, and ZBE reveals a linear decay rate of 0.0083 wt% hydrogen per hour. This is one quantitative measure of catalyst activity decay. The data for the plot incorporate three different catalysts or combinations used to process a PAMCO liquid at 1500 psig, 435C and LVHST of 2 hours. The data set covers run duration of up to 120 hours of oil-catalyst contact. An air driven hydrogen compressor was installed in the Catalyst Life Test Unit to reduce the costs associated with bottle hydrogen. Minor repairs were made on the oil feed pump. Five experimental runs were made with Shell 324 NiMo/Al catalyst using two feedstocks: (1) 40 wt% EDS/EDS raw solvent and (2) 30 wt% SRC-I creosote oil. The EDS feed oil proved to be rather easily hydrotreated as evidenced by 82 to 100% nitrogen removal, essentially complete desulfurization and no catalyst activity decay during 260 hours of continuous operation. Rapid coking resulted from the highly hydrogen deficient SRC/creosote mixture. The Shell 324 catalyst gave excellent hydrogenation of both liquids by increasing the hydrogen content of the product oils by about 3.8 wt%. This catalyst will be used in future studies; however, a new feedstock consisting of 30 wt% SRC-I/PAMCO process solvent will be assessed for use in catalyst decay mechanism studies."
 
First of all, this is just one "Quarterly report" for the US Department of Energy's Contract Number AC22-79ET14876: "Catalysts for Upgrading Coal-Derived Liquids". Where are the other quarterly reports? More importantly, where is the "Final Report"? 
 
And: The research is, or was, being conducted in Oklahoma, where they might still have one or two little old scrape-and-shove surface mines that are active. In 1978, the most recent year we could find statistics for, Oklahoma produced about one tenth of one percent of our nation's coal. Might as well be in Japan. It's roughly the same as if the DOE had assigned a research project into the liquefaction of  prairie grass, scrub brush and slaughter house renderings to West Virginia University.

Coal Conversion Scientist

Far too late, we introduce you to some of the work of Coal-to-Liquid conversion pioneer Frank Derbyshire.
 
He had a career, that ended too soon, marked by milestones of achievement in the science of converting abundant coal into scarce liquid fuels.
 
We enclose, following, a few selections from his catalogue of published research. You will see that he started with Mobil Oil, where he researched for them the science of coal-to-liquid conversion. Some of his discoveries might now be embodied in Exxon-Mobil's MTG (r), Methanol-to-Gasoline, technology, wherein the methanol is synthesized from coal.
 
He later continued his research into coal conversion at Penn State University, as evidenced by reference to two of his works included below.
 
He went on to work, until his death, at the University of Kentucky's Center for Adavnced Energy Research, whom we have cited previously as developers of coal-to-liquid conversion art.
 
We thus submit a few of Derbyshire's publications, just as more evidence that coal-to-liquid conversion is very real technology; technology that could, if we centered our will upon the goal, help us, the US, to achieve liquid fuel self-sufficiency and thus restore some level at least of national prosperity.
 
As follows: