Tasks reported on this term include optimization of chlorided Pt- alumina catalysts, testing of the optimum Pt/Cl alumina catalysts, preparation and testing of zirconia superacid catalyst. (VC)

In this report, we present an improved, feasible and potentially cost effective method of cleaning and beneficiating ultrafine coal. Increased mechanization of mining methods and the need towards depyritization, and demineralization have led to an increase in the quantity of coal fines generated in recent times. For example, the amount of {minus}100 mesh coal occurring in coal preparation plant feeds now typically varies from 5 to 25% of the total feed. Environmental constraints coupled with the greatly increased cost of coal have made it increasingly important to recover more of these fines. Our method chemically modifies the surface of such coals by a series of gaseous phase treatments employing Friedel-Crafts reactions. By using olefins (ethene, propene and butene) and hydrogen chloride catalyst at elevated temperature, the surface hydrophobicity of coal is enhanced. This increased hydrophobicity is manifest in surface phenomena which reflect conditions at the solid/liquid interphase (zeta potential) and those which reflect conditions at the solid/liquid/gas interphases (contact angle, wettability and floatability).

The main objectives of this proposed research work are to refine further the inverse liquid chromatography technique for the study of surface properties of raw coals, treated coals and coal minerals in water, to evaluate relatively surface properties of raw coals, treated coals and coal minerals by inverse liquid chromatography, and to evaluate flotability of various treated coals in conjunction with surface properties of coals. Coals such as Pittsburgh seam coal, Illinois No. 6 coal, Wyodak coal are chosen as representatives of high-rank bituminous coal, high volatile bituminous coal and subbituminous coal, respectively. Coal minerals such as pyrite and dolomite are chosen as representative coal minerals.

The Gas Suspension Absorber (GSA) system brings coal combustion gases into contact with a suspended mixture of solids, including sulfur-absorbing lime. After the lime absorbs the sulfur pollutants, the solids are separated from the gases in a cyclone device and recirculated back into the system where they capture additional sulfur pollutant. The cleaned flue gases are sent through a dust collector before being released into the atmosphere. The key to the system's superior economic performance with high sulfur coals is the recirculation of solids. Typically, a solid particle will pass through the system about one hundred times before leaving the system. Another advantage of the GSA system is that a single spray nozzle is used to inject fresh lime slurry. The GSA system is expected to be the answer to the need of the US industry for an effective, economic and space efficient solution to the SO{sub 2} pollution problem.

Clean Coal Technology implies the use of coal in an environmentally acceptable manner. Coal combustion results in the emission of two types of acid rain precursors: oxides of sulfur (SO{sub x}) and oxides of nitrogen (NO{sub x}). This Clean Coal Technology project will demonstrate a combination of two developed technologies to reduce both NO{sub x} and SO{sub x} emissions: gas reburning and calcium based dry sorbent injection. The demonstrations will be conducted on two pre-NSPS utility boilers representative of the US boilers which contribute significantly to the inventory of acid rain precursor emissions: tangentially and cyclone fired units. Because of cost growth and lack of available funding, no further work has been done after Phase 1 at site B; the wall fired unit.

The original conception of the work was that genetic determinants of the sulfoxide/sulfone/sulfonate/sulfate ( 4S'') pathway in Pseudomonas spp. would be cloned in vivo and then transferred to Thiobacillus spp. This ambition remains an appealing prospect; however, fulfilling that ambition has been confounded by an instability observed in the DbtS{sup +} phenotype in Pseudomonas spp. But the persisting interest in the phenotype has lead to isolation of fresh strains which have a DbtS{sup +} phenotype. One strain in particular, N1-36, has been the focus of extensive characterizations in long-term cultures. During the present quarter, seven cultures maintained in a fermentor'' for a week or longer have been run to determine rate and extent of growth, extent of conversion of dibenzothiophene (DBT) or dibenzosulfone (DBTO{sub 2}) to monohydroxybiphenyl (OH-BP), effect of pH maintained at 6.0, and the effect of adding glucose to cultures in which the amount of glucose had been diminished by bacterial consumption. In addition, a study of the effectiveness of using R68.445 as a vehicle for in vivo cloning of genes was completed this semester, and introduction of DbtS{sup +} determinants into Thiobacillus spp. continues to be an important goal.

Mechanistic explanations have been found for the migration of atoms and ions through the zeolite channels leading to specific distribution of ions and the metal clusters. In this report, we summarize the state of understanding attained on a number of topics in the area of mono- and multimetal/zeolite systems, to which our recent research has made significant contributions. The following topics are discussed: (1) Formation of isolated metal atoms in sodalite cages; (2) differences of metal/zeolite systems prepared by ion reduction in channels or via isolated atoms; (3) rejuvenation of Pd/NaY and Pd/HY catalysts by oxidative redispersion of the metal; (4) formation of mono- or bimetal particles in zeolites by programmed reductive decomposition of volatile metal complexes; (5) cation-cation interaction as a cause of enhanced reducibility; (6) formation of palladium carbonyl clusters in supercages; (7) enhanced catalytic activity of metal particle-proton complexes for hydrocarbon conversion reactions; (8) stereoselectivity of catalytic reactions due to geometric constraints of particles in cages.

The overall objective of the Direct Conversion Technology task is to develop an experimentally verified technology base for promising direct conversion systems that have potential application for energy conservation in the end-use sectors. This report contains progress of research on the Alkali Metal Thermal-to-Electric Converter (AMTEC) and on the Two-Phase Liquid-Metal MHD Electrical Generator (LMMHD) for the period January 1, 1991 through December 31, 1991. Research on AMTEC and on LMMHD was initiated during October 1987. Reports prepared on previous occasions (Refs. 1--5) contain descriptive and performance discussions of the following direct conversion concepts: thermoelectric, pyroelectric, thermionic, thermophotovoltaic, thermoacoustic, thermomagnetic, thermoelastic (Nitionol heat engine); and also, more complete descriptive discussions of AMTEC and LMMHD systems.

This report treats four subject areas: PtCu/NaY and Pd/Cu/NaY catalysts; reducibility of Ni in PdNi/NaY catalysts; CO hydrogenation over PdNi/NaY catalysts; and PdFe/NaY, Ga/H-ZSM5 and PtGa/H-ZSM5 catalysts.

For Pt/NaY catalysts our analysis of the mechanism of metal particle formation has enabled us to produce at will samples which contain either the majority of the Pt particles in supercages, without filling these cages completely, or the Pt particles bulge into neighboring cages. The catalytic selectivity is distinctly different for these preparations, in the former case molecules can enter a supercage which is partially filled by the Pt cluster, in the second case adsorption takes place through the cage window. Applying the same principles of catalyst preparation of bimetallic catalysts enables us to produce PtCu particles in supercages of NaY, which contain, initially a Pt core, surrounded by a Cu mantle. Earlier we have found that Ni ions migrate into hexagonal prisms during calcination of Ni/NaY; this process can be partially suppressed by first filling these prisms with Mn or Cr ions. In more recent work we found that addition of Pt strongly lowers the temperature of Ni reduction. Part of the Ni ions is reduced by hydrogen while still inside the smaller cages. This reduction process is, however, reversible; at elevated temperature and in an inert atmosphere protons re-oxidize the Ni atoms and dihydrogen gas is developed. In …

There are several applications for lasers where the effect of atmospheric turbulence is strong enough to require wavefront compensation, and the compensation can be made by an adaptive optics (AO) system which processes light returned from the target itself. The distribution of the target return light produces limitations to the performance of the AO system. The primary intent of this documentation is to present the new results of an analysis of the anisoplanatic effects arising from target return beacon geometries. It will also lay out the assumptions and steps in the analysis, so that the results can be validated or extended. The intent is to provide a self-consistent notation, simple physical interpretations of the mathematical formulations, and enough detail to reduce the investment of time required to become acquainted or reacquainted with the physics of laser propagation through turbulence, at a level needed to analyze anisoplanatic effects. A general formulation has been developed to calculate the anisoplanatic Strehl of a compensated beam for any beacon distribution and turbulence profile. Numerical calculations are also shown for several beacon geometries and turbulence profiles. The key result is that the spread of the beacon distribution has a much less deleterious effect than does …

The offgas system in the Consolidated Incinerator Facility (CIF) will generate an aqueous waste stream which is expected to contain hazardous, nonhazardous, and radioactive components. The actual composition of this waste stream will not be identified until startup of the facility, and is expected to vary considerably. Wastewater treatment is being considered as a pretreatment to solidification in order to make a more stable final waste form and to reduce disposal costs. A potential treatment scenario has been defined which may allow disposition of this waste in compliance with all applicable regulations. The conceptualized wastewater treatment plant is based on literature evaluations for treating hazardous metals. Laboratory tests hwill be run to verify the design for its ability to remove the hazardous and radioactive components from this waste stream. The predominant mechanism employed for removal of the hazardous and radioactive metal ions is coprecipitation. The literature indicates that reasonably low quantities of hazardous metals can be achieved with this technique. The effect on the radioactive metal ions is not predictable and has not been tested. The quantity of radioactive metal ions predicted to be present in the waste is significantly less than the solubility limit of those ions, but is …

Based on observations made during the operation of the Integrated DWPF Melter System, aromatic organics entering the DWPF Chemical Processing Cell (CPC) can be expected to distribute throughout the CPC Process Vessel Vent System and Mercury Purification Cell. The potential impacts to the operation of the DWPF are discussed.

At the request of Mr. H.L. Brandt and others in the Savannah River Field Office High Level Waste Division office, DWPF, and SRL personnel have reviewed two potential applications for supercritical water oxidation technology in DWPF. The first application would replace the current hydrolysis process by destroying the organic fractions of the precipitated cesium / potassium tetraphenylborate slurry. The second application pertains to liquid benzene destruction. After a thorough evaluation the first application is not recommended. The second is ready to be tested if needed.

This report summarizes the progress and accomplishments of this research project from September 1, 1989 to February 28, 1993. During this period, we have accomplished all of the primary scientific objectives of the research proposal: (1) constructed and evaluated a laser-induced fluorescence detection system that allows direct examination of the chromatographic column, (2) examined nonequilibrium processes that occur upon solute injection and elution, (3) examined solute retention in liquid chromatography as a function of temperature and pressure, (4) examined solute zone dispersion in liquid chromatography as a function of temperature and pressure, and (5) developed appropriate theoretical models to describe these phenomena. In each of these studies, substantial knowledge has been gained of the fundamental processes that are responsible for chromatographic separations. In addition to these primary research objectives, we have made significant progress in three related areas: (1) examined pyrene as a fluorescent polarity probe insupercritical fluids and liquids as a function of temperature and pressure, (2) developed methods for the class-selective identification of polynuclear aromatic hydrocarbons in coal-derived fluids by microcolumn liquid chromatography with fluorescence quenching detection, and (3) developed methods for the determination of saturated and unsaturated (including omega-3) fatty acids in fish oil extracts by microcolumn …

The second phase of research performed at The Electrosynthesis Co., Inc. has demonstrated the successful removal of nitrite and nitrate from a synthetic effluent stream via a direct electrochemical reduction at a cathode. It was shown that direct reduction occurs at good current efficiencies in 1,000 hour studies. The membrane separation process is not readily achievable for the removal of nitrites and nitrates due to poor current efficiencies and membrane stability problems. A direct reduction process was studied at various cathode materials in a flow cell using the complete synthetic mix. Lead was found to be the cathode material of choice, displaying good current efficiencies and stability in short and long term tests under conditions of high temperature and high current density. Several anode materials were studied in both undivided and divided cell configurations. A divided cell configuration was preferable because it would prevent re-oxidation of nitrite by the anode. The technical objective of eliminating electrode fouling and solids formation was achieved although anode materials which had demonstrated good stability in short term divided cell tests corroded in 1,000 hour experiments. The cause for corrosion is thought to be F[sup [minus]] ions from the synthetic mix migrating across the cation …

The Environmental Protection Department/Environmental Monitoring Section (EPD/EMS) administers the Savannah River Site`s (SRS) Groundwater Monitoring Program. During second quarter 1992, EPD/EMS conducted extensive sampling of monitoring wells. EPD/EMS established two sets of criteria to assist in the management of sample results. The flagging criteria do not define contamination levels; instead, they aid personnel in sample scheduling, interpretation of data, and trend identification. Since 1991, the flagging criteria have been based on the federal Environmental Protection Agency (EPA) drinking water standards and on method detection limits. A detailed explanation of the current flagging criteria is presented in the Flagging Criteria section of this document. Analytical results from second quarter 1992 are listed in this report.

Based on observations made during the operation of the Integrated DWPF Melter System, aromatic organics entering the DWPF Chemical Processing Cell (CPC) can be expected to distribute throughout the CPC Process Vessel Vent System and Mercury Purification Cell. The potential impacts to the operation of the DWPF are discussed.

The ultimate objective of this research has been to uncover novel reagents and experimental conditions for heteroatom removal and hydrogen transfer processes, which would be applicable to the liquefaction of coal under low-severity conditions. To this end, one phase of this research has investigated the cleavage of carbon-heteroatom bonds involving sulfur, oxygen, nitrogen and halogen by subvalent transition-metal complexes. A second phase of the study has assessed the capability of the same transition-metal complexes or of organoaluminum Lewis acids to catalyze the cleavage of carbon-hydrogen bonds in aromatics and hence to promote hydrogen shuttling. Finally, a third phase of our work has uncovered a remarkable synergistic effect of combinations of transition metals with organoaluminum Lewis acids on hydrogen shuttling between aromatics and hydroaromatics. (VC)

This report contains the following appendices: Appendix A - Requirements for Undergraduate Level; Appendix B - Requirements for Graduate Level; Appendix C - Graduate Degree In Environmental Engineering; Appendix D - Non-degree Certificate Program; Appendix E - Curriculum for Associate Degree Program; Appendix F - Curriculum for NCC Program; Appendix G - Information 1991 Teleconference Series; Appendix H - Information on 1992 Teleconference Series; Appendix I - WERC interactive Television Courses; Appendix J - WERC Research Seminar Series; Appendix K - Sites for Hazardous/Radioactive Waste Management Series; Appendix L- Summary of Technology Development of the Second Year; Appendix M - List of Major Publications Resulting from WERC; Appendix N - Types of Equipment at WERC Laboratories.

The original conception of the work was that genetic determinants of the sulfoxide/sulfone/sulfonate/sulfate (``4S``) pathway in Pseudomonas spp. would be cloned in vivo and then transferred to Thiobacillus spp. This ambition remains an appealing prospect; however, fulfilling that ambition has been confounded by an instability observed in the DbtS{sup +} phenotype in Pseudomonas spp. But the persisting interest in the phenotype has lead to isolation of fresh strains which have a DbtS{sup +} phenotype. One strain in particular, N1-36, has been the focus of extensive characterizations in long-term cultures. During the present quarter, seven cultures maintained in a ``fermentor`` for a week or longer have been run to determine rate and extent of growth, extent of conversion of dibenzothiophene (DBT) or dibenzosulfone (DBTO{sub 2}) to monohydroxybiphenyl (OH-BP), effect of pH maintained at 6.0, and the effect of adding glucose to cultures in which the amount of glucose had been diminished by bacterial consumption. In addition, a study of the effectiveness of using R68.445 as a vehicle for in vivo cloning of genes was completed this semester, and introduction of DbtS{sup +} determinants into Thiobacillus spp. continues to be an important goal.

In February, 1990, the Secretary of Energy, James Watkins approved a grant for a waste (management) education and research consortium program by New Mexico State University (NMSU) to the US Department of Energy (DOE). This program known by the acronym, ``WERC`` includes NMSU, the University of New Mexico (UNM), the New Mexico Institute of Mining and Technology (NMIMT), Navajo Community College, the Los Alamos National Laboratory and the Sandia National Laboratories. The program is designed to provide an integrated approach to the national need via the following: (1) Education in waste management to reach thousands of students by the three Consortium universities and the affiliate college resulting in graduate, undergraduate, and associate degrees with concentration in environmental management. (The term waste or environmental management is used in a broad sense throughout this paper and includes all aspects of environmental management and environmental restoration.) (2) Professional development via teleconference for industry and government. (3) Technology development programs at the leading edge, providing training to students and information to faculty feeding into the education programs. (4) Education and technology development at the campuses, as well as from four field sites. (5) Ties with other multidisciplinary university facilities. (6) Ties with two National …

This report contains a summary of a High Intensity Solar Cell (HI Cell) development carried out under the NIST/DOE Energy-Related Invention Program. The HI Cell, or Edge-Illuminated vertical Multi-junction Solar Cell, eliminates most major problems encountered with other concentrator solar cell designs. Its high voltage and low series resistance features make it ideally suited for efficient operation at high intensities. Computer modeling shows efficiencies near 30% at 500 suns intensity are possible with state-of-art processing. Development of a working model was largely successful before encountering an unexpected problem during the last fabrication step with the anti-reflection coating. Unfortunately, funding was exhausted before its resolution. Recommendations are made to resolve the AR coating problem and to integrate all the knowledge gained during this development into a viable prototype model. The invention will provide the technical and economic performance needed to make photovoltaic systems cost-effective for wide use.

There is a need to reduce emissions from conventional wood stoves in the short-term while stove replacement takes place over the longer term. One possible is to use fuels that would burn cleaner than cordwood. Densified fuels have been commercially available for years and offer such a possibility. The objective of this project was to evaluate the emissions and efficiency performance of two commercially available densified log types in homes and compare their performance with cordwood. Researchers measured particulate matter (PM), carbon monoxide (CO), and volatile organic matter (VOC) emissions. Both total VOC and methane values are presented. Each home used an Automated Woodstove Emissions Sampler system, developed for the EPA and Bonneville Power Administration, in a series of four week-long tests for each stove. The sequence of tests in each stove was cordwood, Pres-to-Logs, Eco-Logs, and a second, confirming test using Pres-to-Logs. Results show an average reduction of 52% in PM grams per hour emissions overall for the nine stoves using Pres-to-Logs. All nine stoves displayed a reduction in PM emissions. CO emissions were more modestly reduced by 27%, and VOCs were reduced 39%. The emissions reduction percentage was similar for both types of stoves.