WV Coal Member Meeting 2024 1240x200 1 1

More Coal Liquids Analysis

  
Herein is more analysis of the liquid fuels/fuel precursors produced by the H-Coal liquefaction process in Kentucky.
 
What we find most interesting is the final sentence in the abstract: 

"Joseph T. Joseph and John L. Wong

Department of Chemistry, University of Louisville, Louisville, Kentucky 40292, USA


Received 29 January 1980.  


Abstract

Three H-Coal liquids, ASO, ASB, and VSO, have been characterized by quantitative FT-n.m.r. spectroscopy. FT-parameters were chosen to allow determination of aromatic:aliphatic carbon ratios to within 1% and 2% error of the theoretical and the absolute number of aromatic and aliphatic carbons in a simulated coal liquid, respectively. The aromaticity, fa, the Car:Cal ratio and, the absolute number of both the aromatic and the aliphatic carbons on a per mol basis, have been derived for each H-Coal liquid using c.m.r. in combination with other physical data. By analysis of the chemical shifts of the c.m.r. spectra, the carbon distributions in the H-Coal liquids have been estimated and compared in terms of six structural types. The molecular parameters thus derived are reasonable correlated with the average molecular structures proposed as working hypothesis for the molecular characterization of the three H-Coal liquids.

This is part of a series of studies on the molecular characterization of coal-derived liquids supported by the Kentucky Institute for Mining and Minerals Research."

This report is part of a series. Where is the rest of the series, and what more have we learned? When and where will we apply what we've learned?

 

Ashland Synthetic Oil


 
We have told you Ashland Oil's participation in the "H-Coal" synthetic fuel operations in Kentucky, and of their apparent subversion of that pilot plant to, ultimately, supply Hydrogen to one of their subsidiary petroleum refiners.
 
We have also delivered some rather technical information concerning accounts of corrosion problems encountered in coal-to-liquid conversion plants.
 
As it happens, Ashland was at least thorough enough to document that same problem in the H-Coal facility, as in the attached article, excerpt following.
 
Our supposition is that Sasol long ago surmounted all these difficulties, and only await being asked to help us solve them ourselves - if, indeed, we actually do want them solved, so that we can proceed on a sensible path towards a United States liquid fuel self-sufficiency based on coal.
 
All the evidence we have uncovered so far strongly indicates that we, or at least some powerful influencers in the shadows around us, don't want it, else we would, like South Africa, have long ago had it.
 
As follows:
 
"H-Coal Pilot Plant: University of Kentucky Institute for Mining and Minerals Research - findings from the corrosion-monitoring program at the H-Coal Pilot Plant
 
 
1983 May 01
 
Ashland Synthetic Fuels, Inc., KY (USA)
 
One objective of the H-Coal Pilot Plant was to evaluate materials of construction and establish guidelines for materials for commercial application. In order to meet that objective, a Corrosion Monitoring Program was begun in May 1980. The University of Kentucky Institute for Mining and Minerals Research (IMMR), under ASFI Subcontract HC-59, prepared corrosion coupons for exposure in various areas of the H-Coal process, primarily in the high pressure hydrogenation section, but also including the atmospheric fractionator and sour water and sour gas areas. A total of 33 racks consisting of combinations of 32 different alloys were exposed during four different exposure periods (approximately 200 coupons per exposure period) from May 1980 to November 1982. The coupons were exposd to four different types of coal: Kentucky No. 11, Illinois No. 6, Kentucky No. 9, and Wyodak coal separately and/or in various combinations. To extract as much data as possible, the coupons were examined by various techniques including weight loss determination, metallographic examination and microanalytical examination. The original data, results of the various examinations, trend analysis, discussion of meaningful correlations, and conclusions are presented in this report."
 
Once again,very detailed stuff about a technology that, in the United States, at least, officially doesn't seem to exist.

Libya and H-Coal


 
We earlier reported on the H-Coal Coal-to-Liquid conversion technology, and it's pilot plant reduction to practice in Kentucky.
 
There are more confirming documents, as we told you, and we await any expression of interest before sending them along.
 
But, we found this one piece to be of special intrigue, and we think, upon review of the author's bona fides, you'll understand why.
 
Comment follows:
 
"Molecular weight distributions and size fractionations of H-coal liquids

Mohammed Mahfooz Khan

Department of Chemistry, Al-Fateh University, PO Box 13203, Tripoli, Libya


Received 21 October 1981. 
Available online 12 August 2003.

Abstract

This Paper deals with a comparative study on the use of gel permeation chromatography (g.p.c.) and vapour pressure osmometry (v.p.o.) to obtain molecular weight data for the hexane-soluble fractions of three H-coal liquids. The use of two types of column packing materials, polyvinylacetate and styrene-divinylbenzene copolymer gels, is described. A successful, preparative use of the polyvinylacetate gel to fractionate the hexane-soluble fraction of H-coal liquid, atmospheric still overhead (ASO), has been established. Molecular weight data obtained by v.p.o. for the benzene-soluble fraction and the pyridine-soluble fraction of the three H-coal liquids are reported. Solvent extraction has been utilized also to find the amount of oil, asphaltenes and asphaltols in the three H-coal liquids.


The work described in this Paper was carried out at the Department of Chemistry, University of Louisville, Louisville, Kentucky 40208, USA."

1951 - US Bureau of Mines

We can include no links in this dispatch, but, somewhere in our GUV's archives, there should exist a full copy of the paper represented by the following abstract, which we believe to be a true and valid reproduction:
 
"BATCHELDER, H. R., DRESSLER, R. G., TENNEY, R. F., SKINNER, L. C., AND HIRST, L. L.  Role of Oxygen in the production of Synthetic Liquid Fuels From Coal.  Bureau of Mines Rept. of Investigations 4775, 1951, 15 pp.

                   Steps in the production of O2 by the liquefaction and fractionation of air are discussed.  All commercial designs involve the following basic steps:  (1) Supply of air into the plant apparatus; (2) refrigeration of the apparatus; (3) heat transfer between ingoing air and outgoing products; (4) removal of impurities from the air supply; (5) fractionation of liquefied air into components N2 and O2 and delivery of both as product gases; (6) removal of C2H2.  Characteristics of 4 commercial-size plants in this country for the production of O2 are presented, and the type and size of 4 other plants under construction are listed.  The relationship of O2-plant size to plant cost and to O2 cost is discussed.  Increases in O2 cost are quite rapid as the size of the plant is reduced:  $7.00 for a 100-ton plant; $4.80 for 300 tons; and $3.50 for 1,000 tons.  The function of O2 in the production of synthetic liquid fuels is primarily the gasification of coal with O2 to produce mixtures of CO+H2, which then may be used directly, in the case of the Fischer-Tropsch synthesis, or as a source of H2 for coal hydrogenation.  Among the potential advantages of the substitution of O2 for air in the coal-gasification step are the following:  (1) Fuel economy; (2) increased capacity of equipment; (3) wider range of possible fuels; (4) greater adaptability to pressure operation; and (5) higher range of attainable temperatures.  The amount of O2 necessary to produce synthetic fuel by Fischer-Tropsch is about 690 lb. per bbl. of liquid fuel.  This amount of O2  Each change of $1.00 per ton for O2 will change the cost per bbl. of synthetic fuel from this process by about $0.35.  In the coal-hydrogenation process, a relatively large part of the required H2 is to be recovered from the tail gases by low-temperature separation and produced by reforming the product CH4 with steam.  Thus, the O2 requirement for coal gasification is only a fraction of that for Fischer-Tropsch.  About 90 lb. of O2 will be required to make 1 bbl. of synthetic fuel by coal hydrogenation.  At $5.00 per ton, the O2 cost would amount to about $0.22 per bbl. of oil and at $3.00 to about $0.14.  Each change of $1.00 per bbl. in O2 cost will change the cost per bbl. by about $0.04." at $5.00 per ton would amount to $1.72 per bbl. and at $3.00 to $1.03.

We're sending this along to you because it seems a very detailed, very specific cost analysis of one specific component of industrial coal-to-liquid processes, both Fischer-Tropsch synthesis and direct hydrogenation, which are named in the abstract as if they were established and well-known industrial practices. The costs won't be the same nowadays - things have changed since the year you were born, haven't they, Mike? - but the price of oil has gone up a tad, too, hasn't it? We're willing to bet the price proportions, relative to a barrel of oil, are likely to be even more favorable, now.

Note, again, the detail - and this analysis, for the most part, only involves the Oxygen supply, down to a brief census of oxygen producers. And, they only studied the O2 supply since it enables production efficiencies and increased product ranges relative to plain old, freely available, air. But, they also discuss where the Hydrogen for actually transforming coal into a liquid hydrocarbon will come from: CH4 - methane - is produced by the gasification process, apparently, thus exits in the tail gas and can be "reformed", broken down, with steam, with H2 as a product in volumes that will fulfil most of the process requirements; otherwise, it seems, H2 can be derived from the synthesis gas itself.

Explicit, useful data on the science of converting coal into liquid fuel in the US. From 1951.

More proof that we've know how to fulfill our liquid fuel needs, with domestic coal, for many decades. There have to be reasons we haven't been, and are not yet, doing just that; but they cannot, we insist, be good reasons.

Direct Liquefaction of Sawdust in Tetralin

 
 
We herein offer yet more evidence that carbon dioxide emitted by coal-to-liquid, direct-liquefaction processes can be offset by the inclusion of cellulose in the CTL/BTL feed. Other references specify that cellulose (i.e., sawdust, cotton, old Intel's, etc.) can be added to the coal for co-processing into liquid fuels. In such combinations, inclusion of the cellulose actually helps to reduce the generation of some by-products that might be produced if coal were processed alone.
 
The excerpt:

"The Direct Liquefaction of Sawdust in Tetralin

Authors: G. Wang ;  W. Li;  H. Chen; B. Li
Affiliation:  State Key Lab of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, P.R. China

 

Abstract

Hydrogen liquefaction of sawdust in tetralin was performed in an autoclave at below conditions: temperature range from 200°C to 350°C; initial cool hydrogen pressure range from 4 to 10 MPa; reaction time range from 10 to 100 min. The effect of variables on the process of sawdust liquefaction was examined. The results indicate that the oil yield may range from 6.8 to 67.1% at different liquefaction conditions. Temperature has a remarkable effect than initial cool hydrogen pressure and reaction time on the process of sawdust liquefaction. With increasing temperature (200°C-350°C) the conversion, gas yield, H2 consumption and oil yield are all increased, but the yield of preasphaltene and asphaltene (PA + A) increases first (200°C-300°C) and then decreases (300°C-350°C). The high heating value of the products is higher than that of the feedstock. With the increase in initial cool H2 pressure (4-10 MPa), the conversion and gas yield are almost unchanged, the oil yield increases (36.86-57.06%), while the yield of PA + A decreases (28.07-16.27%). With increasing reaction time (10-100 min), both the conversion and the product distribution change little. The existence of H2 or tetralin improves both the conversion of sawdust and the oil yield."
 
We'll note that "oil" yields of sawdust alone in this process are lower than other studies have reported for sawdust combined with coal. The synergy was noted by the other researchers, who posited that the cellulose acted, in addition to the tetralin, as a Hydrogen donor for the coal. And, it might well be that, not only does sawdust - cellulose - enhance the conversion coal into useable liquids, but coal does the same for cellulose. They both "work" better together than either alone, as far as efficiency of production goes, while cellulose also helps to reduce co-production of asphaltene and offsets some of the CO2 generated.
 
And, again, "tetralin", as noted above, has been specified by West Virginia University as the best solvent so far identified for direct coal liquefaction.