We very recently made separate report on this US Department of Energy's Coal Liquefaction project, designated as DE-AC22-94PC93054.
We submit this additional information on that project, through two links, one above and one following, with accompanying excerpts, because we think they present some "illumination" which deserves emphasis.
As customary, we insert and append comment.
However, as a foreword, we urge you to make note of a few things explained in the bodies of the excerpts that might not have been clear in our other expositions of this tax-funded project, and to attend to our opening question, as follows:
First, the supervising DOE entities for this project were, as detailed below, the Federal Energy Technology Centers in Morgantown, WV, and Pittsburgh, PA.
Second, Consolidation Coal, Consol, of Library, PA, was one of the lead contractors.
Another major contractor was WVU, as in, below: "various coal liquid samples and relevant characterization data were supplied to the University of West Virginia".
So, a major, multi-year effort jointly sponsored and supervised by the two local offices of the Federal Department of Energy, in Pittsburgh and Morgantown, led by the region's major coal producer, Consol, and relying on technical support from at least one of the region's two largest centers of higher learning, WVU, proceeded to develop technology that would use the region's, and the nation's, most abundant energy resource, Coal, to fulfil our most urgent energy need, liquid fuel, and we, the US citizens resident in US Coal Country, haven't heard a thing about it.
As follows:
"A Characterization and Evaluation of Coal Liquefaction Process Streams
Reporting Period: 1/1/1997 to: 3/31/1997; Report Issue Date: 04/22/1998
Authors: G. A. Robbins, S. D. Brandes, G. W. Heunisch, R. A. Winschel
CONSOL Inc RESEARCH & DEVELOPMENT 4000 BROWNSVILLE ROAD LIBRARY, PA 15129
This is the Technical Progress Report for the eleventh quarter of activities under DOE Contract No. DE-AC22-94PC93054. It covers the period January 1 through March 31, 1997. Described in this report are the following activities:
• CONSOL characterized process stream samples from HTI Run ALC-2, in which Black Thunder Mine coal was liquefied using four combinations of dispersed catalyst precursors. These results are described in the Results and Discussion section of this report. • Oil assays were completed on the HTI Run PB-05 product blend. Background information is presented in the Results and Discussion section of this report. The results are presented in Appendix 1. • Fractional distillation of the net product oil of HTI Run POC-1 was completed. Background information is presented in the Results and Discussion section of this report. The results are presented in Appendix 2. • CONSOL completed an evaluation of the potential for producing alkylphenyl ethers from coal liquefaction phenols. Those results are described briefly in the Results and Discussion section of this report.
• At the request of DOE, various coal liquid samples and relevant characterization data were supplied to the University of West Virginia and the Federal Energy Technology Center.
• The University of Delaware is conducting resid reactivity tests and is completing the resid reaction computer model. A summary of Delaware's progress is provided in the Results and Discussion section. • The University of Delaware was instructed on the form in which the computer model is to be delivered to CONSOL (Appendix 5). • The University of Delaware submitted a paper on the resid reactivity work for presentation at the 213th National Meeting of the American Chemical Society, April 13-17, 1997 in San Francisco, California. The paper, “Kinetics of Hydroprocessing of Coal-Derived Vacuum Resids”, is appended (Appendix 6).
EXECUTIVE SUMMARY
CONSOL characterized process stream samples from HTI Run ALC-2, in which Black Thunder Mine coal was liquefied using four combinations of dispersed catalyst precursors. The major conclusions from CONSOL’s analyses of samples from HTI Run ALC-2 follow.
• Oil properties were nearly constant for the four run conditions. This consistency implies stability in the operation of the new distillation system and suggests that there was little difference in performance of the four catalyst systems tested. • Coal and oil properties provided no insight into the reasons for solids separation problems with toluene extraction and pressure filtration observed during the run. • Most toluene-extracted solids (TES) and toluene-extracted oil (TEO) samples contained more than a few percent toluene, as received by CONSOL. CONSOL characterization confirmed generally poor extraction in the early part of the run. However, extraction appeared to be moderately successful in periods 3, 9, 12, 13. • The tetrahydrofuran (THF)-soluble fraction of the continuous vacuum still bottoms (CVSB) sample from Condition 4, period 21, was analyzed to determine if Ni or Mo was present in oil-soluble form. The occurrence of Ni and Mo in the THF-solubles is coincident with the occurrence of a trace amount of ash; thus, the Ni and Mo ar e not believed to be organically associated. • The first-stage separator overhead (SOH1) oils and reduced-pressure still overhead (RPSOH) oils had very high concentrations (perhaps 25%) of phenolics . They are potential sources of phenolic chemical feedstocks. • The properties of the hydrotreated product oils showed that the in-line hydrotreater (HTU) was effective for removal of phenolics and most of the aromatics. HTI's data showed the HTU also effectively removed sulfur and nitrogen. • There appeared to be a recent change, relative to characteristics observed over the past three years, in the characteristics of HTI’s L-814 oil used for run start-up and slurry oil make-up. • Solids rejected during the first condition had apparently high Ni concentrations, the origin of which (analytical artifact or trace contamination) is unknown.
CRUDE OIL ASSAY OF NET PRODUCTS OF HTI RUN PB-05
At DOE's request, CONSOL arranged a crude oil assay on the net products of HTI Run PB-05 (also known as Run 227-97). The crude oil assay was conducted by Inchcape (now Intertek ) Testing Services Caleb Brett Laboratory (Houston, TX) on the net products obtained during operating condition 6 of Run PB-05, in which Hondo resid was coprocessed with Illinois 6 coal. The sample was obtained when the on-line hydrotreater was by-passed.
FRACTIONAL DISTILLATION OF NET PRODUCTS OF HRI RUN POC-1
Inconsistencies in distillation data generated by Conoco and Southwest Research Institute in 1995 on HTI net product oils prompted DOE to request additional tests. CONSOL provided a one-gallon sample of HTI Run POC-1 net product oil to Intertek Testing Services Caleb Brett Laboratory (Houston, TX) for fractional distillation. The results are presented in this report.
PREPARATION OF ALKYL ARYL ETHERS FROM COAL-DERIVED PHENOLS
CONSOL evaluated reactions to synthesize alkyl phenyl ethers from coal liquefaction phenols. The program included a literature review and laboratory chemical syntheses. An extensive literature search identified the Williamson Synthesis and its modifications as the preferred methods to produce mixed ethers from phenols. A variation of the Williamson Synthesis was used to produce phenetole and the ethyl derivatives of the phenolics from a caustic extract of a crude direct coal liquefaction product. Other approaches involving acid catalysts failed to produce ethers. It is recommended that the ethyl ether derivatives of coal liquefaction phenols be synthesized and characterized as a diesel fuel extender. CONSOL will develop a plan to extract phenols, synthesize the ethers and coordinate the fuel characterization upon DOE's approval.
RESID REACTIVITY
The University of Delaware completed a parametric study with two resid samples. Temperature, pressure, residence time, catalyst loading, and resid concentration were explored. Conversion leveled off with time indicating the presence of a non-convertible component. This component was isolated by successive solvent-solubility extractions and subjected to hydrotreating .
The structural molecular model was completed. The computer-generated molecular representations were found to match well the experimental data. The reaction model was assembled for catalytic upgrading of coal resids and is undergoing refinement.
TECHNICAL TRANSFER
The University of Delaware submitted a paper on the resid reactivity work for presentation at the 213th National Meeting of the American Chemical Society, April 13-17, 1997, in San Francisco, CA. The paper, “Kinetics of Hydroprocessing of Coal-Derived Vacuum Resids”, is appended.
INTRODUCTION
This is the Technical Progress Report for the eleventh quarter of activities under DOE Contract No. DE-AC22-94PC93054. It covers the period January 1 through March 31, 1997.
CONTRACT OVERVIEW
The objectives of this project are to support the DOE direct coal liquefaction process development program and to improve the useful application of analytical chemistry to direct coal liquefaction process development. This project builds on work performed in DOE Contract No. DE-AC22-89PC89883. Independent analyses by well-established methods are obtained of samples produced in direct coal liquefaction processes under evaluation by DOE. Additionally, new analytical instruments and techniques to examine coal-derive d samples are being evaluated. The data obtained from this study are used to guide process development and to develop an improved data base on coal and coal liquids properties. A sample bank, established and maintained for use in this project, is available for use by other researchers. The reactivity of the non-distillable resids toward hydrocracking at liquefaction conditions (i.e., resid reactivity) is being examined. From the literature and experimental data, a kinetic mod el of resid conversion is being constructed. Such a model will provide insights to improve process performance and the economics of direct coal liquefaction.
ACTIVITIES IN PROGRESS
• Characterization work is under way on samples from HTI Run PB-04 and work was begun on samples from PB-06. • The development of a kinetic/mechanistic model of resid reactivity is continuing.
RESULTS AND DISCUSSION
In HTI Run ALC-2 (Run 227-100), 1,2 the liquefaction performance of Black Thunder Mine coal was tested with four combinations of impregnated (dispersed) catalyst precursors. A new distillation system and solids separation scheme was employed during the run. Run ALC-2 consisted of 21 operating periods at four
conditions. The run was carried out from November 24 through December 23, 1996. The run was planned to be made under six conditions; however, several problems occurred early in the run that decreased the
number of conditions and catalysts that could be tested to four.
ANALYTICAL STRATEGY
In the analytical work performed by CONSOL, an attempt was made to address the following questions:
• What caused the problems encountered in toluene extraction and pressure filtration during the run? • What can be learned about changes in catalyst concentration on startup? • What do sample characteristics say about : - Catalyst performance differences? - Equipment performance (e.g., distillation system)? 33
In general, most sample characteristics changed little over the course of the run. Thus, there are no period-to-period differences that would suggest a reason for extraction/filtration problems. Furthermore, these results provide no conclusive indication of catalyst performance differences. Combined with the distillate product characteristics, the consistent results at each condition also indicate that distillation system operations and performance were very stable.
DISTILLATE PRODUCT CHARACTERISTICS
Characteristics of the distillate and light oil streams (first-stage (unhydrotreated) SOH, second-stage (hydrotreated) SOH, RPSOH, and RPSB oils) are provided ... . This implies stability in the distillation system and provides no indication of performance differences between the catalysts used in the four run conditions.
The high phenolic -OH concentrations of the first-stage SOH and RPSOH oil samples ... indicate that these streams contain a significant fraction (perhaps 25%) of phenolics. The phenolics are potential sources of relatively valuable chemical feedstocks. The characteristics of the hydrotreated second-stage SOH oil samples relative to those of the unhydrotreated first-stage SOH oil samples indicate that the in-line hydrotreater effectively removes phenolic -OH and most aromatic hydrogen from the product oils."
Title: A CHARACTERIZATION AND EVALUATION OF COAL LIQUEFACTION PROCESS STREAMS
Author: G.A. Robbins; G.W. Heunisch; R.A. Winschel; S.D. Brandes
Publication Date: April 1998; OSTI: 9336; Report: DE--AC22-94PC93054--11; Contract: AC22-94PC93054
Research Organization(s): Federal Energy Technology Centers: Morgantown, WV and Pittsburgh, PA
Abstract: This is the Technical Progress Report for the eleventh quarter of activities under DOE Contract No. DE-AC22-94PC93054. It covers the period January 1 through March 31, 1997. Described in this report are the following activities: (1) CONSOL characterized process stream samples from HTI Run ALC-2, in which Black Thunder Mine coal was liquefied using four combinations of dispersed catalyst precursors. These results are described in the Results and Discussion section of this report. (2) Oil assays were completed on the HT I Run PB-05 product blend. Background information is presented in the Results and Discussion section of this report. The results are presented in Appendix 1. (3) Fractional distillation of the net product oil of HTI Run POC-1 was completed. Background information is presented in the Results and Discussion section of this report. The results are presented in Appendix 2. (4) CONSOL completed an evaluation of the potential for producing alkylphenyl ethers from coal liquefaction phenols. Those results are described briefly in the Results and Discussion section of this report. The full report is presented in Appendix 3. (5) At the request of DOE, various coal liquid samples and relevant characterization data were supplied to the University of West Virginia and the Federal Energy Technology Center. These activities are described in Appendix 4. (6) The University of Delaware is conducting resid reactivity tests and is completing the resid reaction computer model. A summary of Delaware's progress is provided in the Results and Discussion section. (7) The University of Delaware was instructed on the form in which the computer model is to be delivered to CONSOL (Appendix 5). (8) The University of Delaware submitted a paper on the resid reactivity work for presentation at the 213th National Meeting of the American Chemical Society, April 13-17, 1997 in San Francisco, California."
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We some time ago documented for you that residual material, "resid", left by primary coal liquefaction processes undertaken for the USDOE by FMC Corporation, in a New Jersey pilot plant, were sent to a coal liquefaction facility in Spain for further experimental processing. There, they employed, as we understood the documentation, a direct coal liquefaction technology similar to WVU's "West Virginia Process" to extract even more liquid hydrocarbons, from the resid, by using a hydrogen donor solvent.
Herein, the resid, as documented above, was sent to Delaware for further processing. And, as noted, the University of Delaware later made a presentation of their findings to a technical conference in California, which we will later attempt to document for you more fully.
In any case, all of this serves as even more, and more official, confirmation that the technologies exist which would enable the United States to employ her most abundant natural resource, Coal, to satisfy one of her most pressing needs, Liquid Fuel.
Why Coal has not yet been publicly harnessed to that task absolutely defies satisfactory explanation.
