National Center for Clean
Industrial and Treatment Technologies
(CenCITT)
Activities Report: June 1992 - September 1994

Director:
John C. Crittenden, P.E., Ph.D.
CenCITT
Michigan Technological University
1400 Townsend Drive
Houghton, MI 49931

906/487-2798 FAX: 906/487-3292
E-mail: jcritt@mtu.edu

Program Manager:
(Point of Contact)
Peter P. Radecki, P.E.
CenCITT
Michigan Technological University
1400 Townsend
Houghton, MI 49931

906/487-3143 FAX: 906/487-3292
E-mail: ppradeck@mtu.edu

Technology Transfer Director:
John T. Quigley, Ph.D.
Dept. Engineering Professional Development
University of Wisconsin - Madison
432 North Lake Street
Madison, WI 53706

608/265-2083 FAX: 608/265-2293
E-mail: quigley@epd.engr.wisc.edu

Participating Institutions:

Michigan Technological University
Institution Coordinator:
C. Robert Baillod, Ph.D.
906/487-2520
University of Minnesota - Minneapolis
Institution Coordinator:
Michael J. Semmens, Ph.D.
612/625-9857 		University of Wisconsin - Madison
Institution Coordinator:
William C. Boyle, Ph.D.
608/262-1777

December 3, 1994

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Table of Contents

The Center at a Glance
Center Director's Report
Technology Transfer Program
Highlights
Quality Assurance/Quality Control
Project Listing for 1992-1994
Research Project Descriptions
Key Personnel
Other Participants
Scientific Advisory Committee
Center Funding
Bibliography

THE CENTER AT A GLANCE

The Center for Clean Industrial and Treatment Technologies (CenCITT) is a research consortium founded on June 1, 1992 to address clean technology needs of interest to industry, government and the public. Clean technology prevents pollution and minimizes waste. Its implementation starts and ends with industry. Accordingly, the CenCITT mission is to assist industry in pollution prevention by devising clean enabling technologies and process design tools, and by pursuing promising leads in treatment, beneficiation and reuse where prevention is not feasible.

CenCITT is structured with a central administration at Michigan Technological University (MTU). Activities are planned and executed through a Steering Committee comprised of Institutional Coordinators at its member institutions (MTU, University of Wisconsin-Madison, and University of Minnesota-Twin Cities), the Technology Transfer Director and the Program Manager. CenCITT's ambitious research program is guided by a truly extraordinary external Scientific Advisory Committee. Currently, 15 departments and/or administrative units participate in CenCITT projects across the three-campus consortium.

CenCITT's main activities fall into three Focus Areas: Clean Process Advisory System (CPASTM), Chemical Reaction Pathways, and Efficient Materials Utilization (EMU). Each Focus Area is comprised of a group of coordinated projects which address a national priority pollution prevention research need. Each Focus Area concept and research program has undergone substantial internal and external reviews. Management and coordination of each are led by a participating researcher. CenCITT's administration,directorate and advisory committees act as facilitators for the creation and maintenance of these "grass roots" collaborative programs. In addition to the Focus Areas, CenCITT has underway several one- and two-year research projects to extend cutting-edge separation and treatment technologies to pollution prevention/clean technology applications. Finally, CenCITT conducts one-year exploratory projects to act as "idea incubators" for possible future focus areas and industrial surveys to prioritize research needs and characterize solution methods. In the same way as exploratory projects become Focus Areas, it is envisioned that the existing Focus Areas will eventually become self-supported, long-term programs developing clean enabling technologies and design tools of broad applicability and industrial practicality. As this occurs, new exploratory projects will be commissioned.

CenCITT's Technology Transfer Program starts at research project conception and continues throughout the life of each project, thus making industry a working partner with the researchers as well as a recipient of end results. To facilitate this continuing collaboration, CenCITT has entered into strategic alliance agreements to codevelop projects and work toward a consensus pollution prevention research agenda with major industrial consortia and are expanding support for small business by establishing relationships with state technical assistance providers. Through these efforts, CenCITT has a blended research and technology transfer program in which results can be communicated to over 200 companies and feedback is received from industry throughout the life of each project.

CENTER DIRECTOR'S REPORT

Advancing pollution prevention through clean technology requires partnering science and technology; engineering and operations; industry and government; humankind and the environment (1). CenCITT joins industry in identifying high priority, widely applicable problems and then structures programs to create innovative tools and technologies with which industrial designers fashion environmentally sound solutions. All research programs are developed in a context of institutional strengths, faculty needs and the dual education/research missions of its participating institutions.

This report generally covers research projects begun between June, 1992 and May, 1994, and technology transfer activities undertaken during this same period. The figure above shows the budget distribution of USEPA funds for the 26 projects involved and are correlated as follows:

These categories will be described later in this report. However, since this is CenCITT's first Director's Report, it is worthwhile to begin with a little history.

HISTORY

Fifteen one-year Startup Projects were commissioned within the first quarter after CenCITT's start date (June 2, 1992). These initial exploratory research and development projects were designed to internally acquaint participants with one another and to identify core strengths at each school.

By April, 1993, SAC had reviewed and commented on these activities, as well as on plans for new and continued activities starting in June, 1993. Based on these reviews, the research results obtained throughout the year and discussions with investigators, 13 one-year projects were commissioned for CenCITT's second year. Three were new projects, while the remainder were continuations of the Startup Projects.

By the time the second SAC meeting was convened (August, 1993), groups of researchers had begun to identify areas of mutual interest. They wrote Concept Papers describing areas of environmental need in industry and which could be addressed at least partially by their groups. These Concept Papers generated the three Focus Areas previously mentioned and later described in the Highlights section of this report. Through concerted efforts toward developing multiple-source funding and external partnerships, these focus areas should broaden their scopes and levels of effort, and eventually become independent of CenCITT's base grant from USEPA.

Much effort is necessary to insure these future directions are industrially practical and of lasting significance. CenCITT's industrial surveys and one-year exploratory projects serve to augment the focus area programs and define new potential focus areas.

UNPRECEDENTED OPPORTUNITY

Today's business climate is highly competitive, and markets are becoming extraordinarily dynamic and difficult to predict. Universities nationwide and the defense sector are experiencing substantial budget cuts. Government is under increasing pressure to demonstrate accountability in its funding programs as well as in its environmental regulatory policy. These factors have put pressure on all sectors to utilize their tight research budgets in non-traditional ways. Accordingly, there is perhaps an historically strong commitment in all sectors to leverage resources and develop partnerships.

Because these developing partnerships involve industry, universities and government, joint consideration of environmental challenges involving all stakeholders is taking place at a level never before possible. We have the opportunity, therefore, to structure efforts to realistically prioritize and address broad environmental problems as opposed to finding narrowly focussed, single media or single discipline quick fixes.

THE CenCITT APPROACH

Finding true solutions requires decision makers to assess three moving targets: our understanding of how the environment works, the economy, and the state of technology. An acceptable environmental plan, therefore, is based on a clear understanding of the means, both economic and technological, to achieve a high-priority environmental dividend. Thus, for CenCITT to "assist industry in pollution prevention," it must have as a core component the ability to consolidate information and modeling tools for all three targets. Furthermore, it must have a means to connect this core component to those in need, from policy makers to industrialists and researchers. CenCITT's Focus Area approach, which first defines industrial clean technology needs and then fashions research solutions, was devised to make this information flow an integral part of research.

The up front honing of research programs through the concept paper process has the effect of coordinating CenCITT programs with ongoing activities at member schools, in industry and government. It avoids duplication of effort as the process is designed to identify similar efforts going on elsewhere and work to establish cooperative relationships with them.

In many ways, this approach is unusual for university-based operations which frequently go from their areas of technical expertise to finding compatible industrial needs. It is, however, very compatible with industrial process and product engineering and research; so much so that two major industrial consortia, the Center for Waste Reduction Technologies (CWRT) of the American Institute of Chemical Engineers and the National Center for Manufacturing Sciences (NCMS), have signed Strategic Alliance Agreements with CenCITT to develop industry-acceptable innovative waste reduction technologies, educational programs, information systems and processes.

Through these alliances, their governmental connections, and a number of other corporate and governmental relationships developed by individual CenCITT researchers, an industry/government/academia virtual research organization has been created which is capable of identifying a consensus research agenda for selected clean technology/pollution prevention topics. This virtual research organization possesses the wherewithal and agility to very quickly establish the interactions and amass the expertise and financial resources to initiate critically important research and technology transfer programs.

RESULTS

An example of what this virtual research organization has done is the transition in less than a year of the Clean Process Advisory SystemTM from a first draft of a concept paper to a program involving a dozen university-based researchers, five corporate development partners and funding in excess of $ 1 million per year. Our Chemical Reaction Pathways activities have generated a new understanding of the relationship between pollution generation and catalyst formulation, as well as patents for new catalysts. The Efficient Materials Utilization, Separation Technologies and Industry Survey projects are providing valuable insights into both the capabilities and limitations of new technologies to enable source reduction, beneficiate materials and recycle would-be wastes.

Currently, direct cost share from participating institutions, industry, government and others, and in-kind participation from codevelopment projects translate to a level of effort more than double that generated by USEPA's annual base grant. CenCITT's success can be measured in the following:

In addressing an environmental challenge, we may find a solution; perhaps we find we did not understand the challenge; perhaps we could find no solution. Whatever the case, it is of fundamental importance that while we seek understanding and solutions, we recognize that our personal contributions are transitory. Involvement in the process by educators, and future engineers, scientists and decision makers is the means by which we make environmental considerations part of the fabric of how industrial designs are created and how our society meets its needs. Through the education of 108 students and the participation of 31 university faculty and staff through May, 1994, USEPA and the rest of CenCITT's funding partners have demonstrated commitment to this concept. Together, we not only conduct clean technology/pollution prevention research, we influence a new generation to think in terms of sustainable engineering.

This model of cooperative research will likely set the standard for addressing the scientific, economic, and socio-political challenges faced by American industry as it moves toward environmental sustainability in the global marketplace. CenCITT is committed to the nurturing and controlled growth of its industry/university/government virtual research organization and invites participation from other like-minded individuals and organizations.

TECHNOLOGY TRANSFER PROGRAM

CenCITT's Training and Technology Transfer (T3) strategy includes outreach programs and internal communication goals for each year of operation. Internal communication among CenCITT participants is promoted as a first step toward team building. External T3 involves commitments to communication between researchers and industry, and to the creation of environmental educational opportunities at all levels. It is a two-way transfer which translates to rapid implementation of R&D accomplishments and research that stays focused on industrial needs. It is an ongoing development and a large part of the CenCITT objective to facilitate the changing needs of industry, the environment and society at large.

Communications with CenCITT participants has been facilitated through the use of five electronic mail (e-mail) lists which utilize the computer networks of the participating universities and companies. These e-mail lists have been particularly beneficial in the rapid communication of timely information and in the mailing of the monthly internal newsletter CenCITTalk.

Internal program development activities have been conducted to promote integration of this multi-campus interdisciplinary faculty-student research team effort. Included thus far have been three teleconferenced faculty/student research seminars, two CenCITT-wide future research projects workshops, and a research specialty conference on Membrane Technology. In addition, the rotation among host campuses of Scientific Advisory Committee convocations has encouraged intercampus exchange among all participants.

CenCITT's external communications are structured to move CenCITT in the direction of self-sufficiency through the creation of industrial consortia, cooperative agreements and partnerships. Early efforts in this regard have involved canvassing industrial firms, and government and academic entities for their clean technology and pollution prevention needs. CenCITT participated in more than 40 specific briefings/ presentations/seminars with industry groups, professional societies, association conferences, educational workshops, and other related professional and technical groups. Based on leads from these activities, CenCITT participants have visited individual companies, toured their facilities and held specific research needs discussions. In addition, more than 150 companies have been surveyed by telephone and/or mail for their specific interests in CenCITT's research projects.

The greater awareness of CenCITT research activities generated by these communications has already led to discovery of a number of areas for collaboration with external participants, A state-funded project to identify clean technology needs for Michigan Industry has led the way in promoting regional outreach for CenCITT. Specific initiatives have also been made with the States of Wisconsin and Minnesota to promote further recognition of CenCITT objectives in regulatory and development agency planning. With its commitment to assisting not only large companies, but small businesses as well, CenCITT has recently become an Associate Member of the National Pollution Prevention Roundtable, an organization comprising most of the state pollution prevention technical assistance providers and strong participation from USEPA and other federal entities.

CenCITT researchers routinely provide input and recommendations in pollution prevention/clean technology research needs conferences. A partial list includes:

Participation in many other conferences and technology transfer events have occurred. For a fairly complete list, refer to the Bibliography section of this report.

HIGHLIGHTS

The Clean Process Advisory SystemTM (CPASTM) is a joint industry/university/government program to create a process and product design system which will provide designers with a means to rapidly examine design alternatives including little-known alternatives which may be more environmentally benign. Information which should be available through this computer-based framework includes new technology and equipment performance and costing data, experience-based guidance, and usable health, environment, safety and risk data, and regulatory information. CPAS is meant to address the challenge of incorporating environmental considerations into conceptual process design where it is felt that the majority of cost-effective waste reduction can be accomplished. Currently, nine CPAS design modules are under development by CenCITT and CWRT members, with a first prototype release scheduled for 1995.

In its development, CPAS utilized the strengths of several independent design module development projects undertaken during CenCITT's first two years of operation. The next step was the development of the strategic alliances with the participation of key SAC members in order that the industrial aspects would not be overlooked. A major step in the progress of CPAS has been the planning of a national meeting (Dallas, October 1994) to collaboratively define a wide range of CPAS tools with diverse input from industry, university and government participants. The meeting's sponsors are CenCITT, CWRT and NCMS.

The Efficient Materials Utilization for Pollution Prevention (EMU) group utilizes unique expertise from all three CenCITT consortium schools and the strengths developed in the first two years of CenCITT operation. In working to assist selected industries in meeting pollution prevention goals, EMU focusses on the development and implementation of technologies to reduce or eliminate industrial and post-consumer solid waste materials. Studies include investigation of physical and chemical differences of materials to enable the development of new materials separation processes and materials characterization studies to find technologies for modifying, minimizing and utilizing both secondary and post consumer materials.

The Chemical Reaction Pathways for Pollution Prevention group is concentrating on the prevention of byproduct formation during the manufacture of chemical products. Projects include the development of worldwide and long-range planning models for the chemical industry at large, catalytic reaction synthesis to predict the formation of hazardous substances, catalytic reactor design, and process design to develop methods for managing trace contaminants in industrial process designs. Accomplishments of the Chemical Reaction Pathways group include a method to predict the trace contaminants in the manufacture of olefins and the development of new highly selective catalysts which for which a patent application has been submitted.

In addition to the three Focus Area Programs, CenCITT has active Exploratory Research Projects which are being funded with the intention of identifying their potential for elevation to Focus Area Program status. They are:

QUALITY ASSURANCE/QUALITY CONTROL

CenCITT's Quality Assurance/Quality Control Plan (QA/QC) has been formulated and approved by the EPA and the SAC. The plan is implemented at the project level by each Project Investigator. The plan is tailored to integrate with the characteristics of each project. For example, projects which do not include experimental data collection (e.g. modeling, process simulation, industrial needs surveys) will not have an experimental QA/QC plan. The intellectual quality of such projects is overseen through a peer review process. QA/QC procedures for projects which include experiments and data collection normally consider the accuracy of results required for the stated intention of the work. For example, a study to examine industrial feasibility of a pulping process would normally not require reagent purities as high as those demanded by catalytic reaction product determinations. Screening experiments may not require as many repeat experiments as pure component property measurements. Each SAC-approved, project proposal normally includes a specific QA/QC plan and names a Project QA/QC Officer. These officers report to their respective Institutional Coordinators, with programmatic oversight by the CenCITT Director.

Since almost all of CenCITT's exploratory research includes participation from graduate and undergraduate students, QA/QC is as much an educational process as a set of experimental guidelines. CenCITT's goal is to emphasize quality in such a way that it becomes second nature to all students involved with its projects. Therefore, a Project Engineer, has been assigned to assist faculty in working with student investigators. Through this engineer's efforts and that of others, communication among students throughout CenCITT can result in constant improvement of individual QA/QC plans and analytical procedures.

A highlight of the QA/QC program was a seminar on the subject presented by CenCITT staff at all three campuses and attended by most of CenCITT's participating graduate students.


PROJECT LISTING FOR 1992-1994

The following is a list of all projects started between 6/92 and 5/94.
Budgets shown include cost share included in CenCITT project accounts.*

Principal Investigator

Project Title		 End Date Current Budget Total Budget
CHEMICAL REACTION PATHWAYS - RELATED PROJECTS
Rudd, Dumesic, Cortright Exploratory Research on the Cleaner Manufacture of Olefins / Predicting the Formation and Buildup of Trace Contaminants in Industrial Catalytic Processes 1994 $142,000 $255,812
Crittenden, Hand Field Testing of a Solar Assisted System for Detoxification of Water 1995 $ 79,321 $ 79,321
EFFICIENT MATERIALS UTILIZATION - RELATED PROJECTS
Ragland, Baker Gaseous Emissions and Ash Characterization from Combustion of Manufactured Wood Products 1995 $ 31,470 $106.470
Hutzler, Dewey Reuse of Granular and Fine Particulate Industrial and Post-Consumer Residuals 1995 $ 75,896 $135,368
Rundman Clean Manufacturing in Foundry Mold and Core Processing 1994 $ 34,730 $ 34,730
Kawatra Agglomeration of Granular and Fine Particulate Industrial Wastes 1994 $ 34,993 $ 62,840
Nesbitt Recycling Lead and Base Metals from Metal Wastes of Brass Foundries 1995 $ 10,000 $ 10,000
CLEAN PROCESS ADVISORY SYSTEM - RELATED PROJECTS
Mihelcic et al. Integrating Models for Predicting Pollution Treatment with Models for the Manufacturing Process 1994 $ 85,410 $168,071
Mullins, Rogers Physical Property Data Needs in Clean Manufacturing Designs 1995 $ 37,696 $ 56,495
Co et al. Process Simulation and Control for Waste Minimization 1994 $ 60,256 $ 60,256
Barna, Rogers, Radecki Pollution Prevention Process Simulator 1995 $105,320 $105,320
SEPARATION TECHNOLOGIES
Hill, Anderson Development of Self-Supporting Microporous Ceramic Membranes for Use in Ultrafiltration, Reverse Osmosis, and Adsorption Processes 1995 $136,140 $236,140
Semmens, Gulliver, Cussler Mass Transfer Behavior of Unconfined Membranes 1995 $168,290 $168,290
Cussler, Semmens Membrane Module Design for Pervaporation 1995 $169,891 $169,891
Maier Process Air Purification by Biofiltration 1995 $136,572 $136,572
POLLUTION PREVENTION NEEDS SURVEYS
Caneba Environmental Aspects of Polymer Formulations 1994 complete $ 12,893
Barna, Diebel, Radecki, Toth Environmental Impact Comparison of Solvent and Kraft Wood Pulping Processes 1994 $ 43,897 $ 43,897
Radecki, Szydlik Clean Technology Opportunities for a Prosperous Michigan 1994 complete $ 70,000


The following are projects initiated after 5/94 (not described in this report)
CLEAN PROCESS ADVISORY SYSTEM - FOCUS AREA
Kim A Case Study: Process Simulation and Control for Waste Minimization 1995 $ 24,806 $ 24,806
Rogers Pollution Prevention Process Simulator: A Physical Properties Resource Tool 1995 $ 54,508 $ 54,508
Hand et al Development of the Effluent Treatment Design Options Tool 1995 $ 9,923 $ 9,923
Barna Design Option Ranking Tool 1995 $ 42,998 $ 42,998
Crowl Process Safety and Risk Evaluation Tool 1995 $ 17,456 $ 17,456
Shonnard, Mayer Environmental Fate and Risk Assessment Tool 1995 $ 24,184 $ 24,184
Barna, Radecki, Rogers CPAS Core Development 1995 $108,639 $108,639
Rogers, Kline Physical Property Predictive Driver 1995 $ 46,874 $ 46,874
Shonnard, Mayer Data for Waste Inventory Factors 1995 $ 46,875 $ 46,875
EFFICIENT MATERIALS UTILIZATION - FOCUS AREA
Hwang et al EMU Laboratory and Administration 1995 $ 72,087 $ 72,087
Dewey et al EMU Assessment 1995 $ 35,665 $ 35,665
Hepworth Thermal Dissociation of Pyrite into Pyrrhotite and Sulfur 1995 $ 37,500 $ 37,500
Ragland Gaseous Emissions and Ash Characterization from Combustion of Manufactured Wood Products 1995 $ 37,500 $ 37,500
CHEMICAL REACTION PATHWAYS - FOCUS AREA
Rudd, et al. Chemical Reaction Pathways for Pollution Prevention 1995 $156,250 $156,250
Rudd, Trevino Computer-Aided System for Chemical Industry Planning 1995 $125,000 $125,000
EXPLORATORY RESEARCH PROJECTS
Cameron Microbial Production of Propanediols: Pathway Design and Host Selection 1995 $ 50,010 $ 50,010
Olson, Sutherland Environmentally Conscious Design and Manufacturing 1995 $ 65,067 $ 65,067

* CenCITT project accounts include cost share such as cash contributions, academic release time, overhead reduction and other forms which are validated by the research administrations of the consortium institutions. Many of the projects include additional cost sharing which are not part of the CenCITT project accounts. Examples include in-kind contributions committed by letters from sponsoring organizations, visiting engineers, and parallel projects where multiple accounts/sponsors are administered by the same principal investigator.


RESEARCH PROJECT DESCRIPTIONS

CLEAN PROCESS ADVISORY SYSTEM AND RELATED PROJECTS

Integrating Models for Predicting Pollution Treatment with Models for the Manufacturing Process: J. R. Mihelcic, A. S. Mayer, D. W. Hand, C.C. Nesbitt, D. R. Lueking, T. N. Rogers Michigan Technological University.

(Referenc:s: 1, 2, 31, 34, 42, 49, 50, 58, 60)

Goal: The objective of this project is to develop a pollution prevention tool by assembling reliable advanced pollution treatment models and integrating them with manufacturing process simulators (e.g. ASPEN, HYSIM). The models consist of air stripping, liquid- and gas-phase granular activated carbon (GAC), chemical precipitation, and biological wastewater treatment which can be used to predict the fate of organic and inorganic pollutants. The software development includes modules for both incorporation into process simulators and stand alone packages.

Rationale: Currently there is much interest by the regulatory community in quantifying air, water, and solid pollutant emissions from waste treatment facilities and by the industrial community in estimating the fate and treatability of specific potential pollutants produced during various phases of the manufacturing processes. The goal of both communities is to effectively reduce production of difficult and costly to treat pollutants and optimize destruction of pollutants easy to treat in a cost effective and environmentally safe manner. Before this goal can be achieved, reliable mathematical models which describe industrial manufacturing and pollution treatment processes must be developed and coupled into a user-friendly modular form.

Approach: This project is aimed at developing advanced pollution treatment models and integrating them with industrial manufacturing process simulators. Models are being developed for conventional wastewater treatment, air stripping, and carbon adsorption. In addition an experimental method needs to be developed which allows estimation of the biokinetic rate constants required for modeling conventional wastewater treatment. The software is being developed for each unit process as a stand alone package. In addition, some examples are shown where modules are incorporated into existing process simulators.

Status: A model for predicting fate of VOCs (volatile organic chemicals) in conventional wastewater treatment plants was developed and was incorporated into a process flowsheet simulator package. In addition an empirical model was developed for studying fate of metals during conventional wastewater treatment. The project was not able to develop a reliable model for predicting metal precipitation. An experimental method was developed which allows measurement of biokinetic parameters. The method is especially useful for chemicals which give small growth rates. Software to Estimate Physical Properties (StEPP) has been designed and developed. StEPP provides access to the following chemical properties: vapor pressure, infinite dilution activity coefficient, Henry's constant, molecular weight, normal boiling point, liquid density, molar volume, refractive index, aqueous solubility, octanol water partition coefficient, liquid diffusivity, and gas diffusivity. Aeration System Analysis Program (ASAP) was developed to simulate stripping processes, such as packed tower aeration, surface aeration, and bubble aeration. In addition, the Adsorption Simulation Software was developed to model multicomponent adsorption of chemicals in fixed-bed adsorbers. This package includes several adsorption models linked to databases which provide the user with chemical and adsorbent properties. Finally, ASPEN user Fortran models for air stripping and catalytic oxidation were implemented with validation by the StEPP air stripping calculations using the Fortran model. Procedures were also developed for placing users' modules into the ASPEN calculation framework. Final reports are available for all of the above, except StEPP, ASAP, and the Adsorption Simulation Software. Final reports and user manuals for these three items will be available by the end of the year.



Physical Property Data Needs in Clean Manufacturing Designs: M.E. Mullins, T.N. Rogers, Department of Chemical Engineering, Michigan Technological University.

(References: 32, 91, 92, 93, 105)

Goals: This project is intended to provide four primary deliverables: (1) a survey of clean manufacturing and environmental data needs by industry, EPA, and CenCITT; (2) to assemble and evaluate relevant data, and provide access for specific CenCITT projects and all the participating investigators; (3) evaluate existing or develop new modelling tools to fill data gaps; and (4) explore the data exchange protocols for incorporating the DIPPR 911 database into commercial process simulators or modules developed under CenCITT.

Rationale: The proposed efforts fall into CenCITT's focus area of pollution prevention design tools, "Improved acquisition and prediction of chemical and Physical Properties of Process chemicals and pollutants." This project has an impact on improving process performance predictions, fate assessment, and risk assessment. If integrated with process simulation models it will enhance their performance in clean manufacturing designs. It is the quintessential "enabling technology," since via interaction with other CenCITT projects it will touch upon most of the other focus areas. For selecting a treatment technology a waste's properties are usually required. Physical properties are also necessary to develop complete material and energy balances for integrated processes.

Approach: The investigators interact with the AIChE/DIPPR program, the CenCITT participants and EPA to develop a comprehensive survey of the data needs for clean manufacturing. We will also make the DIPPR physical property data available to CenCITT investigators in a manner which complies with DIPPR program restrictions via computer data sharing and direct communications. A physical property database is developed and maintained to support other CenCITT projects. Several modelling tools developed for this project are being made available to CenCITT project members.

Status: Major accomplishments include: a compilation of environmental properties for over 1500 compounds (e.g.- partitioning properties, group contribution breakdowns, and other data of environmental interest). This database has been put together to support the development of Software to Estimate Physical Properties (StEPP) by a companion CenCITT project under Dr. Mihelcic of MTU. Some of this database has been used to support other CenCITT projects currently underway. The continuing survey of data needs has been presented at the American Chemical Society Meeting in San Diego in March, 1994. We have acquired the hardware necessary to set up a DIPPR "domain" and anonymous FTP site for the MTU SUN computer network to support our database and share information electronically with other CenCITT members. This system is now being tested.

Process Simulation and Control for Waste Minimization: T. B. Co, N. Kim, D. W. Hubbard, T. N. Rogers, Michigan Technological University.

(References: 44, 88)

Goals: The main objective of this project is to develop a simulation and modeling platform to aid in optimizing waste reduction in chemical processing plants. The platform is to provide appropriate tools for waste reduction studies and retrofits. These tools include standard evaluation criteria of "clean manufacture," an efficient man-machine interface, and dynamic information links among environmental databases, simulators, on-line process monitoring devices, object-oriented models, and expert advisory systems.

Rationale: Waste reduction at the source needs to be enhanced prior to investigating "end-of-pipe" treatment methods. Source reduction can be achieved either by modifying the flowsheet, the reaction process, or the processing methods. Thus, manufacturing plants need to be treated as a whole system because of integrated mass and energy balances, especially when recycle streams are present. Existing simulators potentially provide a cost-effective means of exploring different alternatives of increasing waste reduction. To enhance the capabilities of simulators in the area of waste reduction, we need to supplement them with: (1) evaluation and monitoring tools that allow quick identification of problem areas and P2 opportunities; and (2) diagnostic tools supported by environmental database capabilities and expert advisory systems for generating tested waste reduction solutions.

Approach: The proposed platform will consist of the following: a monitoring/diagnosis module, a design module, a process/data module, and a support module. The monitoring module is to include a tomography system in which the concentration levels of different waste components can be visualized using a user-defined spectral color range, where the color red implies a danger zone while the color green implies a safe zone. The design module is to include an expert advisory system which would suggest solutions geared toward process retrofit, process substitution, and/or intermediate treatment methods. The process/data module consists of data generated by simulators and pilot plants. In this module, existing simulators are enhanced by introducing an object-oriented visual interface. Lastly, the support module includes access to databases (e.g., EPA, OSHA, DIPPR, ISO9000), a knowledge base (e.g., macros and expert rules), and a control base (e.g., models and process control schemes). In order to develop a platform appropriate to industry applications, the tools will be checked on various systems. These are expected to include traditional chemical processing plants such as refineries and specialty chemical processes, and non-traditional processing plants such as paper manufacturing and plastic recycling operations. The modules and the platform will also be developed to support and conform with other modeling projects within CenCITT.

Status: The simulation platform is currently being developed using two formats: one for VAX/VMS format and another for Windows 3.1. The tomography system is already completed. It allows the user to assign color schemes for different compounds depending on the application, and it also includes a simple, icon-based flowsheet maker. The links can then be made to either a steady-state simulator or a dynamic simulator. In the Windows 3.1 format, different windows containing the flowsheet can be opened for each waste component, which then display the concentration levels of that component in the various unit processes. Through the development of the support module, database links to the platform have also been explored. Specifically, physical properties of waste reduction and P2 significance can now be compiled and linked to simulators such as ASPEN and SpeedUP. Finally, modeling and control issues are being explored using pilot plant studies of a polydimethyl siloxane (PDMS) reactor system. So far, a mathematical model of the reactor's heat transfer characteristics, including heat transfer coefficients, has been developed. The next step is the inclusion of expert systems in the simulation platform for diagnostic and advisory functions, together with the appropriate links to the other modules.

Pollution Prevention Process Simulator: B.A. Barna, T.N. Rogers, P.P. Radecki, Michigan Technological University

(References: 5, 34, 83, 101, 102, 104)

Goals: This project was started to provide a core framework in which to house the arsenal of environmental simulation and design tools which will be created under future projects sponsored by CenCITT.

Rationale: Conceptual design and pollution control have traditionally been done at different stages in the development of a process. However, if the designer was given the tools to view a process's environmental impact at the very beginning of the design process, emphasis could be placed on pollution prevention and the selection of the environmentally sound alternatives. This could help eliminate total pollution output as well as reduce the costs of the end-of-the-pipe treatment which is currently done. The Optimizer for Pollution Prevention, Energy, and Economics (OPPEE) started the development of such tools.

Approach: The concept of pollution prevention at the design stage started by OPPEE has grown into a much broader project called the Clean Process Advisory SystemTM (CPASTM). CPASTM has a number of complementary components which comprise a tool group: The Incremental Economic and Environmental Analysis Tool which compares a process's pollution, energy requirements, and economics, an information-based Separation Technologies Database, and an Environmental Fate Modeling Tool. Pollution Prevention Process Simulator activities have been merged into the CPASTM Design Comparison Tool Group.

Status: The following tasks have been completed in the past year. A database of over 800 articles has been collected. These articles focus primarily on pollution prevention, fugitive emissions, stochastic modeling, factored estimation techniques, and cost estimation.

The cost estimation information has been entered into a separate database to act as the economic engine for the Incremental Analysis tool. This database has the cost correlations for over 1000 pieces of equipment from a wide range of sources.

The equipment types include the following: compressors, blowers, vans, vacuum equipment, pumps, vessels, heat exchangers, motors, furnaces, and pollution control equipment.

A Visual Basic program has been started which combines the economic and fugitive emission information collected. The program will allow an incremental analysis to be done on a project showing the changes in both economics and pollution cost of competing processes.

With respect to module integration and testing, new FORTRAN modules have been developed for ASPEN. These modules have been tested to investigate the capabilities of ASPEN's Model Manager for detailed simulation efforts. This work will be continued by looking at stochastic analyses of statistically uncertain process inputs and ranking indices.

CHEMICAL REACTION PATHWAYS AND RELATED PROJECTS

Exploratory Research on the Cleaner Manufacture of Olefins and Predicting the Formation and Buildup of Trace Contaminants in Industrial Catalytic Processing: J.A. Dumesic, D. F. Rudd, University of Wisconsin-Madison

(References: 17, 18, 19, 20, 21, 26, 48,113, 114, 115)

Goals: Hydrocarbon cracking is the major source of olefins. Unfortunately, this technology is also a major source of trace pollutants. The objective of this project is to develop catalysts that are economically competitive and less polluting.

Rationale: Research and development programs in the chemical industry are judged by their ability to develop economically viable and environmentally compatible new technology. Most often the new technology is based on the discovery of active and selective heterogeneous catalysts. We have developed the experimental and theoretical techniques required to create such industrially important catalysts.

In the fuels and petrochemical industry, low value hydrocarbons are converted by catalysts into the cleaner and more reactive hydrocarbons required in the manufacture of motor fuels and chemicals. An important technology is the production of valuable olefins from less valuable hydrocarbons by catalytic cracking. Unfortunately, the current technology produces a wide variety of by-products and trace pollutants. For example, the catalytic cracking of isoheptane produces seven major chemical products of economic importance, eight minor chemical products of little economic importance that must be handled safely, and 62 trace pollutants.

Approach: The Englehard Corporation provided samples of acidic zeolite catalysts, experimental data on the activity and selectivity of these catalysts for hydrocarbon cracking and partial financial support for our efforts to identify the surface chemistry which determines the catalytic properties of acidic zeolite catalysts. It is known that steaming acidic zeolite catalysts changes drastically the rates of formation of the major reaction products that determine the economic viability of the catalytic technology. Also catalyst steaming drastically changes the rates of formation of trace contaminants which are of serious concern as pollutants. We have shown that these phenomena are the direct result of changes in the energy of stabilization of carbenium ions relative to protons on the catalyst surface.

Status: Accurate predictions have been made of the rates of production of all of the major and minor cracking products and of many of the trace pollutants. We are now in a position to determine the catalyst modifications required to reduce the formation of the trace pollutants while maintaining the production of the valuable olefin products. Engelhard Corporation is continuing the funding of research and development at the University of Wisconsin to identify the specific catalytic materials to implement these discoveries.

Field Testing of A Solar Assisted System for Detoxification of Water: J.C. Crittenden, D.W. Hand, Yin Zhang, Michigan Technological University

(References: 6, 7, 9, 22, 38, 51, 61, 62, 65, 69, 70, 71, 72, 73, 74, 75, 76, 81, 82, 89, 106, 107, 108, 109, 118)

Goals: The major objective of this work is to design, build, and test a pilot plant for groundwater remediation. Photocatalysis, an innovative technology, is used in this project with supported catalysts.

Rational: A photocatalytic process is not only able to mineralize many toxic organic compounds, but also effectively destroys nuisance color, taste and odor compounds. The process can be used to remove certain naturally occurring organic matter which are the precursors of the formation of trihalomethanes (THMs) during the chlorine disinfection step of drinking water treatment. Additionally, the process can be solar-powered and used as on-site treatment, and therefore, avoids the risk of transporting and handling potentially hazardous wastes (e.g. spent carbon or resin). Large-scale field trials of longer duration are essential for the engineering design and performance evaluation of photoreactor systems. Recent field experience has suggested photocatalyst fouling and destruction inhibition may be the major obstacles for the implementation of this technology. Therefore, the identification and development of effective and inexpensive methods of pretreatment will be crucial.

Approach: MTU has made important contributions to the application of photocatalysis. Based on results of laboratory experiments conducted at MTU and the 1993 field test performed at Tyndall Air Force Base, Florida, a pilot scale plant with treatment capacity of 2 gallons per minute (gpm) has been designed. The pilot plant uses the fixed-bed photocatalytic process to treat the groundwater directly or to treat the off-gas from an air stripping tower. The photocatalyst is platinized titanium dioxide (Pt-TiO2) supported on silica gel. The design includes water pretreatment and the photoreactors of different configurations. The UV sources are the solar insolation and tanning lamps. The pilot plant has been designed and built with reactor units so the treatment capacity can be easily scaled up.

Status: The pilot plant is now near the completion of its construction and will be used at several sites for field testing and demonstration.

EFFICIENT MATERIALS UTILIZATION AND RELATED PROJECTS

Gaseous Emissions and Ash Characterization from Combustion of Manufactured Wood Products: K.W. Ragland, University of Wisconsin, A. Baker, USDA Forestry Laboratory

(References: 36, 53, 59)

Goals: (1) Measure gaseous and ash emissions from the combustion of selected manufactured wood products as a function of operating conditions in a laboratory scale fixed bed combustor; (2) obtain correlations between volatile organic emissions (which are expensive to measure at the power plant site), and oxygen, temperature and carbon monoxide (which are routinely measured at the powerplant site); (3) examine the need for changing the manufacturing process for the wood product, if the wood product cannot be burned cleanly; and (4) work with a small boiler manufacturer to improve the design of the system.

Rationale: The wood products industries generate $180 billion in sales annually in the U.S from manufactured products such as plywood, flakeboard, particleboard, hardboard, oriented strand board, papers, and fabricated wood products. The adhesives and other non-wood additives may cause disposal problems. During manufacturing waste trimmings are generated which are used to power the manufacturing process. Eventually these manufactured products are discarded, and increasingly they are being rejected by landfills. Boiler and incinerator facilities are having a difficult time getting permits and meeting performance guarantees because of possible emissions of volatile organic compounds and damage to the boiler due to slagging and corrosion when using manufactured wood products. If the combustion is conducted properly, many of these problems probably can be avoided. If not, then some of the components in wood products need to be changed.

Approach: During the first year experiments were conducted on aspen flakeboard and aspen wood in a 76 mm i.d. by 1.5 m long fixed bed combustor. The boards were cut into 6 mm cubes, and were fed from the top at a constant rate downward onto a ceramic grate. Underfire air and overfire air were used to control the combustion. A gas burner was used for startup. Thermocouples along the wall measured the gas temperature profile. Exhaust gases were sampled with a heated probe and analyzed with a gas chromatograph for total hydrocarbons, and a wet sampling train (BIF method 011) for formaldehyde. Oxygen, carbon dioxide and carbon monoxide were measured continuously and recorded on a computer. Particulates were collected on a filter and analyzed by plasma emission spectroscopy.

During the second year a 120 mm diameter by 5 m long fixed bed combustor was built which provided three seconds residence time, better uniformity, and better simulated an industrial boiler. Southern pine particleboard and southern pine wood were used. The boards were cut into 16 mm cubes. An improved feeder was built. Exhaust gases were sampled with a heated probe and analyzed with a gas chromatograph/ mass spectrometer and continuous oxygen, carbon dioxide and carbon monoxide meters. In addition, it was planned to use laser induced fluorescence for in situ measurement of selected volatile organics, to improve the quality of the measurements. With regard to improving the design of boilers used by manufactured board plants (goal number 4 above), it was planned to work with the G.S. Mill Co. on the design and location of their overfire air jets using the FLUENT computational fluid dynamics code.

Status: Extensive measurements of formaldehyde, higher aldehydes, polynuclear aromatic hydrocarbons, total volatile organics, and particulates were made. Emissions of total hydrocarbons, aldehydes and CO were very sensitive to average combustor temperature and excess oxygen. Hydrocarbon and aldehyde emissions below 10 ppm were achieved with 800oC average temperature at a 3 s residence time in the larger combustor. When the average temperature decreased below 800oC, the emissions increased rapidly. For example, at 600oC and 0.2 % oxygen the formaldehyde was 800 ppm, and at 600oC and 3 % oxygen 50 ppm of formaldehyde was observed. The manufactured wood tends to have higher formaldehyde emissions when the average temperature is below 800oC, while above 800oC the formaldehyde is destroyed in both pure wood and manufactured wood. These laboratory tests reinforce the need to carefully control the temperature and excess oxygen in full-scale wood combustors. If the CO emissions are held below 500 ppm, then the formaldehyde emissions are eliminated. However, high CO does not necessarily mean that the formaldehyde is high because elimination of CO requires a higher temperature than does the formaldehyde. The ash shows high sodium due to the adhesive, which can lead to slagging and corrosion. The flakeboard was tested only in the small combustor and needs to be tested in the large combustor for aldehydes and PAH's using the gas chromatograph/mass spectrometer.

Polynuclear aromatic hydrocarbons were observed with pine cubes when the excess oxygen was less than 1 %, whereas with 3 % excess oxygen the PAH's were eliminated. Benzene up to 750 ppm was measured, naphthalene (two rings) and acenaphthylene (three rings) were observed to 200 ppm, and phenanthrene (three rings), fluoranthene (three rings), and pyrene (four rings) were observed. Comparison between pure wood and manufactured wood with respect to PAH's needs to be conducted. In situ measurement of polynuclear aromatics using laser induced fluorescence but could not be continued due to budget shortfall.

A relationship with the G.S. Mill Co. was developed for input to the emissions needs and furnace design. Furnace design improvements using the FLUENT computational fluid dynamic code are promising but were cut off due to lack of project funding.

This laboratory work builds confidence that in a well designed and operated industrial boiler, the formaldehyde and PAH emissions can be minimized. The study is incomplete because more manufactured wood products need to be studied.

Reuse of Granular and Fine Particulate Industrial and Post-Consumer Residuals: G. R. Dewey, J. F. Sandell, N. J. Hutzler, M.A. Kayser, Michigan Technological University

(References: 12, 13, 14, 15, 16, 23, 24, 25, 35, 41, 59, 77, 78)

Goals: Objectives include developing and demonstrating beneficial utilization protocols that can be used to identify markets and uses for a variety of solid residuals. Detailed characterization techniques using electron beam analytical techniques including digital imaging in conjunction with chemical leaching studies will be used to locate and identify several RCRA metals in municipal waste combustor (MWC) fly ash. Additionally, electron beam analytical techniques coupled with digital imaging will be used along with X-Ray diffraction to evaluate compositional trends corresponding to pozzolanic reactivity in a variety of electric utility coal fly ash samples.

Rationale: The environmental and economic costs of landfilling solid residual materials is making this management strategy increasingly unattractive. Developing beneficial utilizations for solid residuals in construction materials will provide alternatives to landfilling and improve the economic competitiveness of residual generators. Also, increasingly valuable landfill space will be conserved by diverting these materials to alternative uses. Some residuals, because of the presence of leachable RCRA metals above regulatory limits, are difficult and expensive to effectively manage. The development of detailed microscopic characterization procedures can assist in identifying the exact locations and specific compounds responsible for unsatisfactory leaching behavior. This information can be used in efforts to modify industrial processes to isolate or even remove the undesirable compounds. These characterization procedures can also be used to identify desirable phases in some residuals which contribute to their beneficial properties when used in a specific product or utilization application.

Approach: The project activities are divided into two segments: 1) physical testing and experimental work for developing utilization options and 2) chemical and physical characterizations using chemical leaching and electron beam analytical techniques. Physical testing and experimental work includes the evaluation of MWC bottom ash in asphalt pavement materials. These activities also include the testing of MWC and coal fly ash samples using electron beam analytical techniques and chemical leaching of MWC fly ash. Research regarding MWC fly ash has included the focus on identification of lead bearing compounds since this toxic metal currently leaches above limits as outlined in the EPA's Toxicity Characteristic Leaching Procedure (TCLP). Research regarding coal utility fly ash has focused on identification of glass bearing phases which contribute to pozzolanic properties when used as an admixture in portland cement concrete.

Status: Utilization strategies for incorporating MWC bottom ash as an aggregate substitute in hot-mix bituminous mixtures has been successfully demonstrated. A detailed report including recommendations to the Olmsted County Waste-to-Energy facility for a field demonstration pavement has been submitted. Additional laboratory testing of MWC bottom ash as an aggregate substitute in controlled low strength materials (CLSM) has also been conducted with less definitive results.

Leaching studies of MWC fly ash have been completed with results indicating that lead is distributed throughout a wide range of particle sizes and leaching may be dominated by adsorption-desorption mechanisms. A paper discussing this subject has been submitted for review. A continuous method of monitoring metal leachability has been explored for use with this residual. A paper discussing this technique has been submitted for review. The use of various electron beam analytical techniques has shown lead to be located on both the exterior and interior of particles and to be associated with several common elements. A paper discussing these findings has been submitted for review.

The analysis of coal fly ash samples have shown that the spatial distribution of different composition glass phases can be identified using electron beam analytical techniques in conjunction with digital imaging. Results of this work have been published in a refereed proceedings and presented at a national conference.

Clean Manufacturing in Foundry Mold and Core Processing: K. B. Rundman, D. Churches, Michigan Technological University

(Reference: 52)

Goals: The object of this project is to examine the concept of minimizing the waste generated by cores in the casting process through the development of gradiently bonded cores. Project tasks include the study of current coremaking technology, experimentation into the nature of core breakdown during casting, and the production and testing of gradiently bonded cores.

Rationale: Due to the heat of casting, organically bonded cores break down to different degrees, resulting in clean sand grains, resin- and carbon-coated sand grains, small resin- and carbon-coated lumps, and larger, still-bonded core "butts." The larger lumps and core butts are subsequently screened out from the sand system and sent to a landfill. The introduction of gradiently bonded cores could result in the reduction of the amount of waste sent to landfills, as well as a reduction in the amount of binder used in the making of the cores.

Approach: The focus of this study is to gain a better understanding of the breakdown of organically bonded cores and to look at ways to encourage these cores to break down more completely during the casting process. To this end, experiments designed to reveal some of the mechanisms of core breakdown are being conducted both in the MTU foundry and in the foundries of local industries. Understanding breakdown induced be casting heat should result in better engineered cores which break down more efficiently. Gradiently-bonded cores will be tested for strength and handling characteristics, and will be compared to their non-gradient counterparts to evaluate the commercial feasibility of gradient bonding. The main characteristic now considered of importance is the transverse strength, which is similar to the 3-point bend test. These 1" x 1" x 8" test bars are to be made with higher binder content at the outside surface than in the interior; first, the test bars will be made hollow with different levels of binder at the outside, then the bars will be filled in with core material of a lower binder content than at the outside. It is also expected that these gradiently-bonded cores will be tested and evaluated in the casting atmosphere.

Status: To date, several experiments have been conducted into the nature of core breakdown during casting suggesting that the degree of breakdown is dependent on several factors such as: binder type and level, availability of oxygen for combustion, gas flow through the core, temperature of the casting and the amount of heat available for binder combustion. Cores are currently being made in the MTU foundry in an attempt to evaluate the performance of hollow cores with varying binder content and hole size. The effect of moisture on these tests is also being considered.

Agglomeration of Granular and Fine Particulate Industrial Wastes: S. K. Kawatra, Michigan Technological University

(References: 10, 63, 79)

Goals: The project has three main objectives: 1. To improve the removal of inorganic fine particulates from waste streams; 2. To control the composition of the particulate wastes by physical separation, which will simplify utilization while reducing the amount of hazardous waste produced; 3. To improve the handling characteristics of the particulates, by pelletizing them into a coarser, more easily handled and utilized form.

Rationale: Many industries produce wastes that consist of fine particulates, for example coal-fired power plants (fly-ash, and flue-gas scrubber sludge), foundries (bag-house dusts) and chemical plants (wastes from the manufacture of emulsions, pigments, and other colloidal dispersions). It is important not only to remove these particulates from air or water to prevent pollution, but also to recover them in a form that can be utilized easily, so that it will not be necessary to dispose of them in landfills or hazardous-waste dumps. Recovery and re-use of these particulates is complicated both by their small size, which makes removal and handling difficult, and by their highly variable quality. Recovery of these wastes in a purified form, followed by agglomeration into coarser particles, will make their utilization much more industrially attractive. Since production of fine particulate wastes ranges from large tonnages to small quantities, it is also important that the processes developed work equally well on both large and small scales.

Approach: Methods are being developed in this research to agglomerate fines from suspension, using selective oil agglomeration and electroflocculation to collect the ultrafines into loose floccules. The flocculated material is then formed into pellets, which are hardened both by chemical reaction and by sintering so that they can be handled and utilized.

Status: Electroflocculation was investigated for agglomerating silicone emulsions from wastewater. This process was found to be capable of recovering silicones from dilute suspensions with a high enough concentration that they could be recycled directly. Coal fly-ash was treated by a combined oil-agglomeration/froth flotation process to remove carbon, which is a troublesome contaminant which prevents many fly-ashes from being utilized. By using the proper reagents at a dosage of less than 0.5 kilogram/metric ton, the carbon content was reduced from an unacceptable 7% by weight to only 1.8% by weight, which is much less than the 2-4% by weight considered tolerable in most of the existing uses for fly-ash. The de-carbonized fly-ash has also been found to be suitable for formation of high-strength, light-weight sintered pellets, and shows promise for use as a binder component for formation of pellets of other inorganic materials. In particular, the pelletization of iron ore for blast-furnace feed consumes millions of tons of inorganic pellet binder, and so there is a definite market for producing such binders from fly-ash. The study of the use of fly-ash as a pellet binder is being continued with funding provided by the State of Illinois.

Recycling Lead and Base Metals from Metal Wastes of Brass Foundries: C. C. Nesbitt

Michigan Technological University

(References: 11, 45, 95)

Goals: The primary objective of this project is the development and optimization of a process by which brass wastes containing copper, zinc and lead may be recycled in-house or processed into a valuable commodity for resale. The secondary goals of the project were to investigate the feasibility of using hydrometallurgical processing to separate the base metals with the expressed purpose of producing litharge (PbO) from the insoluble lead residues by low temperature calcination.

Rationale: Brass manufacturers have unique environmental problems. The brass wastes (such as buffing wheel lint, machine cuttings, etc.) contain lead which was alloyed with the copper and zinc to improve machinability. The lead concentration may vary from 1-8% by weight; concentrations high enough to give the waste a hazardous rating. The hydrometallurgy of copper and zinc suggests them to be easily recovered in pure form by dissolving in acid or ammoniacal solutions. Lead, on the other hand, is only soluble in nitric and acetic acid or strongly basic solutions. Lead sulfate has a low solubility which may be exploited as a means of separating the Cu and Zn from the lead. Albeit relatively stable, lead sulfate is a hazardous compound. Another form of lead would have to be generated for either recycle or resale. Litharge (red) and massicot (yellow) differ in appearance and crystal structure, but have the same stoichiometric formula (PbO). Both (primarily litharge, however) are used in the manufacture of lead storage batteries, glass and as an analytical reagent in the assay of gold and silver ores. The typical method of production is the high temperature oxidation (~1000oC) of fuming lead. Results from this project could be used to developed a process for the aqueous conversion of lead sulfate to lead carbonate or lead hydroxide which could be converted to PbO at substantially lower temperatures (400-600oC).

Approach: The project research has been divided into two areas--1) development and optimization of the leaching/separation of Cu and Zn from the lead, and 2) development and optimization of a process to produce PbO from the lead-rich leach residue. Brass chips were obtained from the Kohler Company of Wisconsin to use as feed stock for leaching experiments Initially, the optimal leachant had to be determined based on dissolution rate, separability, removal % and ability to reuse the leachants after processing. Sulfuric acid, ammonia hydroxide, hydrochloric acid, chlorine, and cyanide leachants are effective media used to dissolve Cu and Zn; selective leaching of lead by acetic acid may also be an effective process. Thermodynamics of lead in water suggest that lead sulfate, lead carbonate and lead hydroxide are the most stable precipitates which may be formed in solution. Reagent grade lead salts were purchased for experiments to produce PbO by low temperature conversion.

Status: During the past year, many discoveries have been made. Sulfuric acid with air with small amounts of copper ions are present produced the best results in which the leaching of copper and zinc was accomplished in one fifth the leach time required with acid alone. In addition, less than 0.6% of the lead is lost and 100% of the residue was lead sulfate. Sodium carbonate mixed with lead sulfate resulted in complete convert to lead carbonate. Results of roasting studies conducted on lead carbonate found that at low temperatures (400-450oC) complete conversion to PbO (both litharge and massicot) could be accomplished in less than 1 hour. The significance of these results is a novel, low cost process to produce PbO from virtually any lead source (waste or raw material). Further optimization of conditions is required in the upcoming year.

SEPARATION TECHNOLOGIES

Development of Self-Supporting Microporous Ceramic Membranes for Use in Ultrafiltration, Reverse Osmosis, and Adsorption Processes: C.G. Hill, Jr., M.A. Anderson, University of Wisconsin-Madison

(References: 3, 4, 8, 37, 43, 66, 68, 96, 100, 110, 111, 112, 116)

Goals: To fabricate and characterize modules of self-supporting ceramic membranes which have a high ratio of surface area to volume and which can be produced in a cost-effective manner.

Rationale: While ceramic membranes can be employed under conditions where organic polymer membranes are susceptible to rapid degradation (e.g., in applications where high temperatures and organic solvents are employed), commercialization of ceramic membranes has been rather restricted. This situation is, in part, a consequence of their high cost and the low ratio of surface area to volume characteristic of these materials. Normally, ceramic membranes are slip-cast on porous extruded ceramic supports fabricated mostly of alpha alumina. These generally take the form of tubes, but can also be formed as monolithic "honeycomb" structures. The resultant low yield and low ratio of surface area to volume ratio lead to economic situations which favor the use of these materials only in extremely high "value-added" applications.

Approach: A dipping procedure is used to cast suspended colloidal particles onto supporting fabrics which can subsequently be removed by firing. This approach appears to provide an inexpensive route for the preparation of a high-surface area to volume ceramic membrane. The precursor colloidal suspensions of a variety of different metal oxides can be prepared in a wide range of particle sizes. This approach offers opportunities to prepare microfilters, ultrafilters or even reverse osmosis or gas separation membranes using the same technology.

Status: To date we have successfully fabricated materials in the form of sheets which are both self-supporting and sufficiently robust to provide the strength necessary to develop a working module. The next step will be to assemble several of these sheets into a working module. This task remains to be completed. Completion of this task will be required before the data necessary to evaluate this technology can be obtained.

Mass Transfer Behavior of Unconfined Membranes: J.S. Gulliver, M.J. Semmens, University of Minnesota.

(References: 28, 29, 54, 56, 80, 85, 86, 87)

Goals: The goal of this project is to develop mass transfer behavior of hollow fiber membranes that are inserted directly into mixed tank reactors to provide a more efficient and inexpensive contactor for a variety of separations and transfer processes.

Rationale: Hollow fiber membranes having a diameter of about 300 - 400 um can provide a very large surface area per unit volume for mass transfer since a very large number of fibers can be packed into a small volume. This makes this type of membrane ideal for a variety of separation and transfer processes that are commonly used in industry.

In this project novel membrane module designs are investigated to optimize separations that are commonly used in chemical processing and environmental applications. The approach involves taking the fibers out of a small and confining module and placing them directly in a reactor or water body in a manner that ensures good contact and efficient use of the membranes.

Approach: The use of hollow fibers to improve the dissolution or removal processes was assessed by evaluating the ability of the fibers to dissolve oxygen in water in a variety of different mixing regimes. In addition, the use of membranes for free oil or solvent separation from the surface of the water was investigated.

Status: Gas transfer studies: The use of free unconfined fibers in the vicinity of different submerged jets has been studied. A model has been developed to characterize the energy and mass transfer requirements.

Ultrafiltration studies: These studies were abandoned because a well-characterized membrane module could not be located or fabricated.

Solvent Recovery studies: The use of hollow fibers to successfully recover spilled solvents and oils was demonstrated.

Membrane Module Design for the Pervaporation of Acetic Acid: E.L. Cussler, M. J. Semmens, University of Minnesota.

(References: 27, 55, 64, 84)

Goals: The objective of the project is to collect the information required to design and build the best pervaporation module for solvent recovery from aqueous streams. Pervaporation is a process where a liquid mixture is evaporated across a selective membrane, giving a combined selectivity from the difference in volatilities and from the membrane. This membrane is held in a membrane module which keeps the liquid mixture on one side while vapor is removed from the other.

Rationale: We have decided to focus on water saturated with solvent. Organic solvents are widely utilized in industry for the manufacture and cleaning of a variety of products and solvent contaminated aqueous streams are a common and significant problem. For example, in Michigan and Illinois alone the pharmaceutical industry discharges over 10 million pounds of solvents per year. The pervaporation process can be used to recover these solvents by exploiting the differences between chemical and physical properties of the solvents and the water.

Approach: The research approach is split into two initial thrust areas. The first is to find hollow fiber membranes that have the required selectivity to effectively separate the organic solvents from the water in a pervaporation system. A suitable membrane has been found and experiments will be conducted with this membrane in a membrane module. The second thrust is in the design of the module and understanding the best means of applying the vacuum to the membrane. In this study the effectiveness of applying a vacuum to the fiber lumen is being investigated by examining the effects of fiber length and diameter etc. on the membrane performance. A model will be developed to account for mass transport in the vacuum phase. Finally, the designed modules will be applied to the recovery of solvents in water and the performance of the modules will be assessed.

Status: The preliminary work on acetic acid separation that was initiated last year was abandoned since no membranes having a favorable selectivity for acetic acid could be identified. The study was redirected with input from CenCITT to examine the more generic problem of solvents in aqueous streams. The modeling studies to examine the effects of the degree of vacuum, fiber length, fiber diameter etc. on performance are complete and a paper is being drafted on this topic. Experimental studies for solvent recovery are ongoing.

Process Air Purification by Biofiltration: W. J. Maier, University of Minnesota

(References: 30, 90)

Goals: The overall objective of this study is to expand and facilitate engineering applications of the biofiltration process. Biofiltration is a biologically mediated process for removing organic chemicals from contaminated air streams. The specific objectives of the experimental phase of the program were to develop reliable design and operating protocols for extending the application of biofiltration in the context of industrial applications in which zero emissions are the desired goal, as well as providing technology for pollution prevention from small volume sources such as chemical vents, emissions from storage tanks, stationary internal combustion engines, drying operations, and odor control. A related objective is to anticipate the effects of variable loading rates in terms of air flow and pollutant concentrations on removal efficiencies because many of the applications are not continuous but operate on seasonal or cyclical time frame.

Rationale: Biofiltration is an environmentally friendly technology because it results in complete oxidation of pollutants into carbon dioxide and water without generating residual waste streams; it also requires very little energy. It is therefore an attractive technology for pollution prevention by treating and recycling process air streams from manufacturing operations in a closed system. It is however aimed primarily at systems that emit relatively low concentrations such that recovery of chemicals for reuse of the solvent or chemical is not practical or economical.

While current industrial biofilters report removal efficiencies significantly less than 90%, they fall short of obtaining some current and proposed discharge limitation rules. Pushing the technology to its limits so as to meet these more stringent rules will require process optimization through precise understanding of controllable operating variables and more precise engineering design correlations. This project focusses on these issues.

Another important rationale for extending the application of biofiltration is for applications in pollution prevention from small volume sources such as chemical vents, emissions from storage tanks, stationary internal combustion engines, drying operations, and odor control. These sources are frequently time variabled and require that the system be capable of responding after long periods of shut down.

Approach: A coupled program of laboratory testing and mathematical modeling has been carried out. Pilot plant testing was designed to study removal of representative model compounds that are frequently encountered in industrial processing (methyl ethyl ketone, hexane, and xylene) and cover a range of solubility in water (Henry's constant) which affects removal efficiencies in biofilm packed columns. The pilot plant consists of three packed columns operating in series. Sampling ports are located at several points in each reactor to measure concentration distributions of chemicals. The reactors are loaded with ceramic packing to minimize compaction and pressure drop buildup. The packing provides surfaces for attachment of biomass while minimizing increase in pressure drop due to biomass accumulations. A series of process variables studies have been carried out to measure the effects of residence time, inflow concentration, moisture content, and nutrient addition. Measurements of biomass accumulation, endogenous destruction of biomass, and attendant changes in pressure drop have been carried out.

The data generated from the pilot plant are being analyzed using a computer programmed dynamic model for simulating the combined effects of organics removal, accumulation of biomass, and mass balancing of nutrient requirements. The resulting correlations are being used to define optimal strategies for loading the biofilters to avoid excessive pressure drop buildup and avoid the need for cleaning the columns. The concept of switching the flow sequences both for steady state operations and for handling anticipated time dependent changes in loadings is being defined as a means for controlling biomass accumulation.

Status: Pilot plant studies on methyl ethyl ketone have been completed. Studies on hexane and xylene using single reactors are continuing. Initial operations focused on treating air containing a single organic chemical (MEK). Flow/pressure controls and analytical procedures proved to be reliable, however, control of moisture was a problem. Providing a constant flow of completely water saturated air without creating pockets of liquid water in the columns proved to be difficult. A system for recycling a small flow of water containing nutrients was therefore initiated and proved to be effective resulting in stable operations. The columns were loaded with ceramic packing to provide a stable non-compressible support for accumulation of biomass. One drawback of using ceramic surfaces as opposed to peat or related high surface area organic support media is that accumulation of biomass is slow. Removal efficiencies of MEK have increased significantly as biomass accumulation has increased and removal to below detection limits was obtained routinely.

At high inflow concentrations, removal rates in columns with well established biomass films were found to be oxygen limited. The first order kinetics of removal of chemical may therefore be a reflection of oxygen transport limitations; the implication is that increasing biofilm thickness is not beneficial. The implications of oxygen limitation will be examined using the mathematical model.

The effects of switching reactor flow sequences on overall removal effectiveness has not been fully resolved. Questions to be answered relate to defining the effects of endogenous metabolism in grazing down the biofilms that form near the inlet where growth activity is highest. Additional testing is also underway to determine whether moving high biomass reactors downstream can be used effectively to achieve more complete removal of chemical in a temporarily overloaded column system. The rationale is that deeper biofilms are more effective for treating the low concentration air in the downstream reactors because oxygen is not limiting as opposed to the inlet regions where chemical transport is greater than oxygen transport and results in oxygen limitations.

Analysis of biofiltration using a computer model to simulate rates of removal and biodegradation show that non-optimal biomass distribution in the reactors may be responsible for incomplete removal. It has been shown that biomass accumulates in the inlet portion of the reactors while the downstream sections of the reactors contain low biomass concentrations due to slow growth and concurrent endogenous decay. The results of these modeling studies suggest that a manifolded biofilter that allows changing the flow sequence would allow maintaining a more uniform biomass distribution resulting in more complete removal of organics, in the 99+%range. A further advantage of complete removal of organics is that it would facilitate recirculation of process air in manufacturing operations thus allowing closed loop operations with essentially zero discharged to the atmosphere.

POLLUTION PREVENTION NEEDS SURVEYS

Environmental Aspects of Polymer Formulations: G. T. Caneba, Michigan Technological University

(References: 39, 40)

Goals: An objective of this project is a survey and discussion of environmental problems and emerging technologies in polymer formulations. Major polymers and end-use applications will be identified, as well as various additives used in the various formulations. Up to five polymer systems with environmental problems will be identified. Finally, based on these areas of environmental concerns, the possible use of products derived from the free-radical retrograde-precipitation polymerization (FRRPP) process will be considered.

Rationale: The polymer industry is driven primarily by cost and performance. However, the industry faces new environmental challenges to increase recycling, develop biodegradable products, and phase out additives containing heavy metals and ozone-depleting materials. At the same time, there is a need to increase the longterm utility and performance of formulated products.

Approach: The survey of various polymer production figures will be obtained in the literature. Based on level of production and present environmental concerns, polymer systems with environmental problems will be obtained. In order to ascertain the suitability of the application of the FRRPP process, emerging technologies as well as feasibility of the use of this process will be factored in.

Status: The result of the survey indicates that major environmental problems exist in polymer systems used in packaging and in paints and coatings. Major pollution has been found to be based on production of polyvinylchloride, since it requires a substantial amount of additives. In paints and coatings, the problem seems to be in the use of solvents, plasticizers, and other leachable organic additives. In the area of additives, uses of heavy metals as colorants and thermal stabilizers are also of great concern. Based on all these data as well as results of contacts with industry, the FRRPP process could possibly be used in the production of paints and coatings that might not require the use of solvents, plasticizers, and leachable organic additives. It could also possibly be used in the production of various polymeric additives for polyvinylchloride and compatibilizers for recycled resins.

Environmental Impact Comparison of Solvent and Kraft Wood Pulping Processes: B. A. Barna, J. F. Diebel, P. P. Radecki, T. J. Toth, Michigan Technological University

Goals: Wood pulping processes which include organic solvents in their process chemicals have been proposed as causing less environmental impact than the industry standard Kraft process. The objective of this study is to assess the validity of this proposal from a forward-looking perspective.

Rationale: Reducing the environmental impact of wood pulping has historically been the common goal of USEPA and the Pulp and Paper Industry. Methods to achieve this goal can generally be classified as either process modifications or process replacements. One group of process replacement alternatives, Organosolv Processes, uses organic solvents in their process chemicals. Claims of reduced environmental impact from these processes, as compared to the Kraft Process, are usually attributed to the avoidance of sodium sulfide and sodium hydroxide in pulping chemicals, and the ability to avoid chlorine-containing compounds in subsequent bleaching operations. Organosolv processes have been researched worldwide for over 30 years and have been brought to various levels of demonstration from bench-scale to minicommercial-scale, depending on the process.

At the same time, substantial improvements have been made in Kraft technology. In particular, these improvements can be found in secondary water treatment plants, digester designs, and reduction of chlorine-containing compound usage in bleaching operations.

Comparing the state of development of Organosolv and Kraft, with an eye toward potential impact provides CenCITT a valuable industrial assessment to determine if Organosolv development should be a high-priority research area in support of the Forest Products Industry.

Approach: A core work group including MTU investigators and Mr. Salman Aziz of Integrated Paper Services, Inc., Appleton, Wisconsin, generated a set of guidelines to compare several Organosolv processes to Kraft. With input from a worldwide collection of Organosolv process developers, this work group will compile and assimilate necessary data to compare the theoretical environmental impacts of these processes. In addition to plant boundary effluent comparison, information to determine market niches for Organosolv pulps is being investigated.

Due to concern over potential losses of solvent and other process chemicals in Organosolv procEsses, material balances for one process, MTU Organosolv, are being experimentally determined. This kind of information is useful in estimating operating costs for processes which have not yet been field tested.

Status: Literature on various Organosolv processes including ALCELL, ORGANOCELL, MILOX, and MTU Organosolv; as well as the conventional pulping processes of Kraft and sulfite, have been assembled. Citations and keywords have been entered into an interactive database. The process comparison has been completed based on this literature review and several unpublished sources.

Bench-scale digester runs have been completed for a single set of process conditions and pulping chemical strengths for Black Spruce by the MTU Organosolv Process. Chromatographic and combustion analyses of before- and after-digestion pulping chemicals, digester head space gas samples, and pulp and wood samples are being evaluated to close material balances.

Clean Technologies for a Prosperous Michigan: P. P. Radecki, C.R. Szydlik, Michigan Technological University

(References: 46, 47)

Goals: This project was funded entirely by the State of Michigan and Michigan Technological University. Its goal was to assess the needs of Michigan Industry for clean technologies developed by CenCITT and to develop a plan for disseminating R&D results as they are obtained.

Rationale: Making industries important to the Michigan economy more environmentally benign is a central concern to industry, government and the public. Success or failure in this area affects economic competitiveness, public health, ecosystem well-being and quality of life. The establishment of CenCITT, a national center devoted to clean technology, could help to address technical issues facing Michigan companies. Assisting CenCITT to establish efficient means for transferring clean technology research results to industry would facilitate the rapid solution to industrial clean technology challenges.

Approach: A survey of industrial sectors in Michigan which hold high correlation to CenCITT research projects was conducted. Respondents were asked to evaluate the importance of expected outcomes of CenCITT research projects to their companies. This information was fed back to CenCITT researchers for consideration in ongoing and future work. A document was prepared to describe ongoing and proposed CenCITT projects and programs. The document was provided to the Michigan Department of Commerce for dissemination to Michigan Industry.

Status: All work on this project has been completed. The Michigan Industry survey results and a CenCITT research plan were produced. The latter is continually updated and has become the standard technology transfer vehicle for CenCITT. In addition to distribution by the Michigan Department of Commerce, CenCITT has submitted revised copies of the research plan document to over 30 companies, nationwide.

KEY PERSONNEL

Steering Committee

Dr. C. Robert Baillod - MTU
Dr. John C. Crittenden - MTU
Dr. John T. Quigley - UW
Dr. Michael J. Semmens - UM 		Dr. William C. Boyle - UW
Dr. Neil J. Hutzler - MTU
Mr. Peter P. Radecki - MTU


University of Minnesota
Twin Cities
Dr. Edward L. Cussler
Dr. John S. Gulliver
Dr. Malcolm T. Hepworth
Dr. Walter J. Maier 		University of Wisconsin
Madison
Dr. Marc A. Anderson
Mr. Andrew J. Baker (USDA Forestry Lab)
Dr. Douglas C. Cameron
Dr. Randy D. Cortright
Dr. James A. Dumesic
Dr. Charles G. Hill, Jr.
Dr. Kenneth W. Ragland
Dr. Dale F. Rudd
Dr. Walter A. Zeltner
Michigan Technological University
Dr. Bruce A. Barna
Dr. Gerard T. Caneba
Dr. Thomas B. Co
Dr. George R. Dewey
Mr. John F. Diebel
Dr. David W. Hand
Dr. Richard E. Honrath
Dr. Davis W. Hubbard
Dr. Jiann-Yang Hwang
Dr. Surendra K. Kawatra
Dr. Nam K. Kim
Dr. Andrew A. Kline
Dr. Donald R. Leuking
Dr. Alex S. Mayer 		Dr. James R. Mihelcic
Dr. Michael E. Mullins
Dr. Carl C. Nesbitt
Dr. Walter W. Olson
Dr. Anton J. Pintar
Mr. Tony N. Rogers
Dr. Karl B. Rundman
Mr. John F. Sandell
Dr. David R. Shonnard
Dr. John W. Sutherland
Ms. Clare R. Szydlik
Mr. Richard E. Tieder
Mr. Timothy J. Toth
Dr. Yin Zhang


OTHER PARTICIPANTS

Industrial Alliances and Memberships

Center for Waste Reduction Technologies of the American Institute of Chemical Engineers (AIChE)
National Center for Manufacturing Sciences
National Pollution Prevention Roundtable

Industry and Government Collaboration and Cooperation

American Energy Technologies, Inc.
Central Illinois Light Company
Cleveland Cliffs Iron Company
Design Institute for Physical Property Research Consortium of AIChE
Dow Chemical Company
Dow Corning Company
Electric Power Research Institute
Elf Aquitane, Inc.
Engelhard Corporation
G.S. Mill Co., Northborough, MA
Gulf Publishing - Hydrocarbon Processing
Illinois Clean Coal Institute
Integrated Paper Services, Inc.
Ion Electronic
Membran Corporation
Metropolitan Waste Control Commission,
Michigan Department of Commerce
St. Paul, MN
The M.W. Kellogg Company
NASA - Ames Research Center
OLI Systems, Inc.
Olmsted County, Michigan
Shell Development Company
Simulation Sciences, Inc.
State of Illinois
State of Ohio
Texas Instruments, Inc.
3M Corporation
Upper Peninsula Power Co.
USDA Forest Products Laboratory
USEPA Risk Reduction Engineering Laboratory


SCIENCE ADVISORY COMMITTEE

Member

Affiliation

Expertise

George Vander Velde, Ph.D.

Chair

 Golder Associates Hazardous Waste Treatment
James E. Alleman,

Ph. D.

Vice Chair

 Purdue University Biological Treatment

Solids Residuals

Paul L. Bishop, Ph.D. University of Cincinnati Hazardous Waste Treatment

Solids Residuals

Hugh J. Campbell, Jr., Ph.D. E.I. Du Pont De NeMours Physical and Chemical Treatment Processes
Dennis A. Clifford, Ph.D. University of Houston Water and Hazardous Waste Treatment
John J. Convery USEPA Risk Reduction Engineering Laboratory Separation Technologies
Harry Freeman USEPA Risk Reduction Engineering Laboratory Pollution Prevention Research
Darryl W. Hertz The M.W. Kellogg Company Chemical Process Pollution Prevention
Michael C. Kavanaugh, Ph.D. ENVIRON Corp. Remediation of Wastewater
Thomas Keinath, Ph.D.* Clemson University Physical/Chemical Treatment Technologies
Larry Longanecker* USEPA Office of Pollution Prevention and Toxics, E,E & T Division Chemical Process Industry
Karen Morehouse USEPA-ORD Ofc. of Exploratory Research Project Officer
Lawrence L. Ross, Ph.D.* AIChE Center for Waste Reduction Technologies Waste Minimization in Chemical Process Industry
William Thacker, Ph.D. Simpson Paper Pulp and Paper Waste Minimization and

Hazardous Waste Management

Member

Affiliation

Expertise

Clare Vinton National Center for Manufacturing Sciences Environmentally Conscious Manufacturing
Jack Weaver, Ph.D. AIChE - Sponsored Programs Chemical Process Safety, Waste Minimization Operations
Donald J. Walukas, Ph.D.* Concurrent Technologies Corporation Environmentally Conscious Manufacturing
Edward A. Weinbrecht Sandia National Laboratories Environmentally Conscious Manufacturing

* Former Members

CENTER FUNDING

Funding Sources Funds Rec'd*

FY 1993

 Funds Rec'd*

FY 1994

 Totals
EPA core funding 1,000,000 935,000 1,935,000
EPA, other 0 0 0
Other federal 0 0 0
State/local** 84,822 27,956 112,778
Consortium (matching)** 159,730 199,329 359,059
Private sector** 9,516 60,167 69,683
Total funds Received 2,476,520
Total funds Expended 2,170,839
Student Support*** Number

FY 1993

 Number

FY 1994

 Funds

FY 1993

 Funds

FY 1994

Undergraduate 25 25 22,477 38,650
Master's 18 14 153,361 109,767
Doctoral 14 12 61,405 91,844
Post doctoral 1 2 14,497 13,441
Total 58 53 251,740 253,702
Student Support to Date Number Funds
Undergraduate 50 61,127
Masters 32 263,128
Doctoral 26 153,249
Post doctoral 3 27,938
Total 111 505,442


SEE NOTES NEXT PAGE

* These funds include budgets and expenditures for all research projects initiated between 6/92 and 5/94 and expended through FY94, and technology transfer and administration activities ending 5/31/94. Budgets and expenditures for activities begun after 6/1/94 are not included.

** Figures shown include cost share such as cash contributions, academic release time, overhead reduction and other forms which are validated by the research administrations of the consortium institutions. Many of the projects include additional cost sharing which are not part of the CenCITT project accounts. Examples include in-kind contributions committed to by letters from sponsoring organizations, visiting engineers and joint projects in which multiple accounts/sponsors are separately administered by the same principal investigator. This additional cost share is valued at over $500,000.

*** Includes Fringe Benefits for the Master, Doctoral, and Post Doctoral students.

BIBLIOGRAPHY

REFEREED JOURNAL ARTICLES

1. Harrington, J.R., J.R. Mihelcic, R.N. Lewis, and T.L. Planinsec, "FATE: A Computerized Model for Estimating the Fate and Treatability of Hazardous Pollutants in Publicly Owned Treatment Works," Water Environment Technology, Vol. 5, pp. 49-53, 1993.

2. Mihelcic, J.R., C.R. Baillod, J.C. Crittenden, and T.N. Rogers, "Estimation of VOC Emissions from Wastewater Facilities by Volatilization and Stripping," Journal of the Air & Waste Management Association, Vol. 43, pp. 97-105, 1993.

3. Peterson, R.A., M.A. Anderson, C.G. Hill, Jr., "Application of Ceramic Membranes to Reverse Osmosis," Separat. Sci. Technol., 28, 327, 1993.

4. Peterson, R.A., M.A. Anderson, C.G. Hill, Jr., "Development of TiO2 Membranes for Gas Phase Nanofiltration," J. Membr. Sci., 94, 103, 1994.

5. Radecki, P.P., D.W. Hertz, C. Vinton, "Build Pollution Prevention Into System Design," Hydrocarbon Processing, pp. 55-66, August 1994.

6. Zhang, Y., J.C. Crittenden, D.W. Hand, D.L. Perram, "Fixed-Bed Photocatalysts for Solar Decontamination of Water," Environ. Sci. Technol. 28, 435-442, 1994.

7. Zhang, Y., J.C. Crittenden, D.W. Hand, "Solar Photocatalytic Decontamination of Water," Industry & Chemistry, 18, 714-717, September 19, 1994.

ARTICLES SUBMITTED OR IN PRESS

8. Chu, L., G. Yaluris, W.A. Zeltner, and M.A. Anderson, "Microporous Alumino-Silicate Gels Synthesized by Sol-Gel Method," Submitted to Mat. Res. Soc. Symp. Proc., 1994.

9. Crittenden, J. C., Y. Zhang, D.W. Hand, D.L. Perram, "Solar Detoxification of Fuel-Contaminated Groundwater Using Fixed-Bed Photocatalysts" Submitted to Water Environmental Research, July 1994.

10. Kawatra, S.K., and T.C. Eisele, "Removal of Unburned Carbon from Fly Ash by Froth Flotation," submitted to the Society of Mining and Metallurgical Engineering, September 9, 1994.

11. Nesbitt, C.C., S. Xue, "Recycling of Base Metals from Metal Wastes of Brass Foundries," October, 1994.

12. Sandell J.F., G.R. Dewey, L.L. Sutter, J.A. Willemin, "Evaluation of Lead Bearing Phases in Municipal Waste Combustor Fly Ash," submitted to Journal of Environmental Engineering, July 1994.

13. Sandell J.F., G.R. Dewey, L.L. Sutter, J.A. Willemin, "Evaluation of Metal Transport Mechanisms in Municipal Waste Combustors Using Thermodynamic Predictions," to be submitted to Journal of Environmental Engineering, Nov. 1994.

14. Sutter, L.L., J.F. Sandell, G. R. Dewey, "Electron Microprobe and Mineral Liberation Analysis Techniques to Characterize Combustion Residuals," submitted to the Minerals, Metals and Materials Society, TMS.

15. Willemin J.A., G.R. Dewey, J.F. Sandell, L.L. Sutter, "The Influence of Adsorption Mechanisms on Lead and Cadmium Leaching from Municipal Solid Waste Combustor Fly Ash," submitted to Environmental Science and Technology, July 1994.

16. Willemin J.A., C.C. Nesbitt, G.R. Dewey, J.F. Sandell, L.L. Sutter, "Flow Injection Analysis of MWC Fly Ash Leaching Characteristics," submitted to Journal of Air and Waste Management, July 1994.

17. Yaluris, G., R.J. Madon, and J.A. Dumesic, "Microkinetic Analysis of Isoheptane Cracking Reactions on US Y-zeolites," to be submitted to Journal of Catalysis.

18. Yaluris, G., R.J. Madon, and J.A. Dumesic, "Factors Controlling the Selectivity of Isoheptane Cracking Reactions on Olefin-Selective Catalysts," to be submitted to Journal of Catalysis.

19. Yaluris, G., R.J. Madon, D.F. Rudd, J.A. Dumesic, "Catalytic Cycles and Selectivity of Hydrocarbon Cracking on Y-zeolite-based Catalysts," Accepted for publication in Industrial and Engineering Chemistry Research

20. Yaluris, G, J.E. Rekoske, L.M. Aparicio, R.J. Madon, J.A. Dumesic, "Isobutane Cracking over Y-zeolites: Part 1. Development of a Kinetic Model," submitted to Journal of Catalysis.

21. Yaluris, G, J.E. Rekoske, L.M. Aparicio, R.J. Madon, J.A. Dumesic, "Isobutane Cracking over Y-zeolites: Part 2: Catalytic Cycles and Reaction Selectivity," submitted to Journal of Catalysis.

22. Zhang, Y., J.C. Crittenden, D.W. Hand, D.L. Perram, "Destruction of Organic Compounds in Water Using Supported Photocatalysts," Accepted for publication in Journal of Solar Energy Engineering, September, 1994.



BOOKS OR BOUND PROCEEDINGS

23. Dewey, G.R., M.A. Kayser, L.L. Sutter, "Characterization of Electric Utility Coal Fly Ash for Use in Portland Cement Concrete," The Proceedings of the American Power Conference, Chicago, IL, April, 1994.

24. Dewey, G.R., M.L. Movrich, "Municipal Solid Waste Incinerator Bottom Ash as an Aggregate Substitute in Hot-Mix Bituminous Mixtures," Proceedings, FHWA/EPA Symposium on Recovery and Effective Reuse of Discarded Materials and By-Products for Construction of Highway Facilities, Denver, CO, Oct 20, 1993.

25. Dewey G. R., M.A. Kayser, L.L. Sutter, "Microscopic Characterization of Coal Fly Ash for Use in Concrete", Accepted for Publication in The Proceedings of the Fifth International Conference on Fly Ash, Silica Fume, Slag, and Natural Pozzolans in Concrete, Milwaukee, Wisconsin, June 1995.

26. Hand, D.W., Y. Zhang, E.G. Klun, and J.C. Crittenden, "Photocatalytic Decontamination of Water Using Sunlight and TiO2 Impregnated Adsorbent and Non-adsorbent Supports," presented at The First International Conference on TiO2 Photocatalytic Purification and Treatment of Water and Air on November 8-13, 1992. (included in refereed conference proceedings)

27. Jewel, L.J., M.J. Semmens, "Solvent Recovery Using Hollow Fiber Membranes," ASCE National Conference on Environmental Engineering, Critical Issues in Water and Wastewater, Boulder, CO, July 14, 1994.

28. Johnson, D., M.J. Semmens, C.J. Gantzer, "Minimizing VOC and Odor Emissions through Controlled Oxygen Dissolution," Purdue Industrial Waste Conference, May, 1994.

29. Johnson, D., M.J. Semmens, "The Performance of Unconfined Hollow Fiber Membranes as Pipe Flow and Mixed Flow Aerators," ASCE National Conference on Environmental Engineering, Critical Issues in Water and Wastewater, Boulder, CO, July 14, 1994.

30. Maier, W., " Enhancement of Biofiltration for Air Purification," Proceedings 49th Annual Purdue Industrial Waste Conference, May, 1994.

31. Mayer, A.S., V.J. Wildfong, R.A. Voigt, "Modeling the Fate of Hazardous Compounds in Conventional Wastewater Treatment within a Waste Minimization Framework," Proceedings of Envirosoft '94, Computational Mechanics Publishers, Southampton, UK, in press, 1994.

32. Mullins, M.E., Radecki, P.P.,and Rogers, T.N., "Engineering, Chemical Data Correlation," Kirk-Othmer Encyclopedia of Chemical Technology, Volume No. 9, 4th Edition, John Wiley and Sons, New York, (1994).

33. Nesbitt, C.C., C.H. Byers, "Environmentally-benign Materials and Processes," from the Workshop on Innovation in Materials Processing and Manufacture: Exploratory Concepts for Energy Applications, Oak Ridge, TN, March, 1993.

34. Radecki, P.P., "Computer-Based Methods for Finding Green Synthesis Pathways and Industrial Processes for Manufacturing Chemicals: A View From 10,000 Feet," Proceedings Document for the USEPA/ NSF Workshop on Green Syntheses and Processing in Chemical Manufacturing, Cincinnati, OH, October, 1994.

35. Sutter L. L., J.F. Sandell, G.R. Dewey, "Applications of Electron Microprobe and Mineral Liberation Analysis Techniques to Municipal Solid Waste Combustor Fly Ash," Proceedings of the International Symposium on Extraction and Processing for the Treatment and Minimization of Wastes, San Francisco, CA, February 27 - March 3, 1994.

36. Wilkening, R., Evans, M., Ragland, K., and Baker, A., "Emissions From Laboratory Combustor Tests of Manufactured Wood Products", First Biomass Conference of the Americas, Burlington, VT, Sept. 1, 1993.

37. Zeltner, W.A., M.A. Anderson, "Preparation of Nanosize Oxide Particles and Their Coating onto Porous Supports," in Dispersion and Aggregation: Fundamentals and Applications, (B.M. Moudgil, P. Somasundaran, Eds.), Engineering Foundation, New York, 307, 1994.

38. Zhang, Y., J.C. Crittenden, D.W. Hand, D.L. Perram, "Solar Detoxification of Groundwater Using Fixed-Bed Photocatalysts," Presented at Water Environment Federation 67th Annual Conference, Chicago, IL, October 1994.

PROJECT REPORTS

39. Aggarwal, A., G.T. Caneba, "Environmental Aspects of Polymers," Progress report submitted to CenCITT, December 1, 1992.

40. Aggarwal, A., G.T. Caneba, "Environmental Aspects of Polymers," Report submitted to CenCITT, November, 1993.

41. Dewey, G.R., J.F. Sandell, J.A. Willemin, M.L. Movrich, "Utilization of Combustion Residuals Generated by the Olmsted County Waste-to-Energy Facility," Final Report on the Use of Bottom Ash in Bituminous Mixtures submitted to Olmsted County, MN, January, 1994.

42. Herlevich, J., "Air Stripper Model Comparison Results: ASPEN Versus StEPP," Unpublished report, Michigan Technological University, Houghton, Michigan, 1994.

43. Hill, C.G., M.A. Anderson, "Development of Self-Supporting Ceramic Membranes for Fluid-Phase Separations," A report to the Center for Clean Industrial and Treatment Technologies, for period June 1, 1992-May 31, 1993, April, 1994.

44. Kim, N. K., "Dynamic Modeling of PDMS Polymerization Reaction," Submitted to CenCITT in August 1993.

45. Nesbitt, C.C. "Metal Removal by Chemical Precipitation as Insoluble Hydroxides and Sulfides," Unpublished report, Michigan Technological University, Michigan, 1994.

46. Radecki, P.P., C.R. Szydlik, "Volume 1: CenCITT Research Plan," final report submitted to Michigan Department of Commerce/Department of Natural Resources for Clean Technology Opportunities for a Prosperous Michigan project. February 28, 1994.

47. Radecki, P.P., C.R. Szydlik, "Volume 2: Clean Technology Needs Surveys," final report submitted to Michigan Department of Commerce/Department of Natural Resources for Clean Technology Opportunities for a Prosperous Michigan project. February 28, 1994.

48. Rudd, D.F., J.A. Dumesic, "Exploratory Research on the Cleaner Manufacture of Olefins," final report to CenCITT for Closeout of project with same title., September, 1994.

49. Voigt, R.A., A.S. Mayer, "Incorporation of Waste Treatment Models into Process Flowsheet Simulators," Unpublished report, Michigan Technological University, Houghton, Michigan, 1994.

50. Voigt, R.A., A.S. Mayer, "Modeling Metals Fate in Conventional Wastewater Treatment Plants," Unpublished report, Michigan Technological University, Houghton, Michigan, 1994.

51. Zhang, Y., J.C. Crittenden, D.W. Hand, D.L. Perram, "Removal and Destruction of Water Contaminants Using Advanced Oxidation Processes," Monthly Reports to Armstrong Laboratory, the U.S. Air Force (1991-1994).



THESES/DISSERTATIONS

52. Churches, D.C., "Clean Manufacturing in Organically Bonded Foundry Cores," M.S. thesis, Michigan Technological University, Houghton, MI, 1994.

53. Evans, M.A., "Formaldehyde and Polycyclic Aromatic Hydrocarbon Emissions from Particleboard in a Fixed Bed Combustor," M.S. thesis, University of Wisconsin, Madison, WI, 1994.

54. Farmer, R., "Process Variables and Optimization Studies," M.S. thesis, University of Minnesota 1994.

55. Jewel, L.J., "Organic Solvent Recovery Using Membranes," M.S. thesis, University of Minnesota, September, 1994.

56. Schade, B. "Mathematical Prediction and Pilot Plant Analysis," M.S. thesis, University of Minnesota, 1994.

57. Wilkening, R.T., "Emissions from the Combustion of Flakeboard in a Laboratory-Scale Fixed Bed Combustor," M.S. thesis, University of Wisconsin, Madison, WI (1993).

58. Wildfong, V., "A Comprehensive Model to Predict Fate of Volatile Organic Compounds in a Wastewater Treatment Facility," M.S. thesis, Michigan Technological University, September, 1993.

59. Willemin, J. A., "Leaching Mechanisms of Lead and Cadmium from Municipal Waste Combustor Fly Ash," M. S. thesis, Michigan Technological University, Houghton, MI, 1994.

60. Wingard, K.M., "An Innovative Method to Determine Biokinetic Constants to Assist Prediction of Organic Pollutant Fate," Department of Civil and Environmental Engineering, Unpublished Master's Thesis, Michigan Technological University, Houghton, MI, 1994.

61. Zhang, Y., "Detoxification of Water Using Fixed-Bed Photocatalysts," Environmental Engineering Ph.D. thesis, Michigan Technological University, Houghton, MI, 1994.



CONFERENCES AND WORKSHOPS HELD

Between October and December, 1992, three electronic conferences were conducted between the CenCITT founding institutions. These conferences featured on-line computer imagery and audio simulcasting at the three schools. In each conference, CenCITT researchers introduced their research programs and answered questions regarding potential for interaction with other projects.

Three Scientific Advisory Committee (SAC) meetings were conducted: February 1-2, 1993 (Madison, WI), August 2-3, 1993 (Houghton, MI), and April 28-29, 1994 (St. Paul, MN). Each meeting included proposal and/or project presentations by CenCITT researchers. Time was set aside in each for substantial interaction between SAC members and researchers. Campus and laboratory tours were conducted. The last meeting also featured a graduate student poster session.

In June of 1993, an internal specialty conference was held in St. Paul to identify areas of national priority and common interest among CenCITT membrane separation technology researchers. Faculty, staff and students from all three schools participated.

Extensive planning has been underway for a Clean Process Advisory System National Working Meeting to be held in Dallas, TX, October 27-28, 1994. This by-invitation event is planned to involve 80-100 participants from industry, government and universities. It is being hosted by Texas Instruments, Inc. and cosponsored by CenCITT, the Center for Waste Reduction Technologies and the National Center for Manufacturing Sciences.

PATENT DISCLOSURES

62. Hand, D.W., D.L. Perram, J.C. Crittenden, and Y. Zhang, "Destruction of Disinfection By-Product Precursors from Water using Photoassisted Heterogeneous Catalytic Oxidation," Patent Pending, January, 1993.

63. Kawatra, S.K., T.C. Eisele, "Flotation Column with Adjustable Support Baffles," August 9, 1994.

64. Semmens, M.J., "The use of evacuated hollow fiber membranes for oil and solvent spill recovery." Submitted to the University of Minnesota Patents and Licensing Office, Spring 1994.

65. Zhang, Y., J.C. Crittenden, D.W. Hand, D.L. Perram, "Photocatalytic Oxidation of Organic Contaminants in Fluid," US Patent Application, No. 08/160,102, Filed on Nov. 30, 1993.



PRESENTATIONS MADE

66. Anderson, M.A., C.G. Hill, Jr., A.Ali, L. Chu, R.A. Peterson, E.T. Webster, "Ceramic Membranes for Novel Separations," Eighth Symposium on Separation Science and Technology for Energy Applications, 1993.

67. Cameron, D.C., "Benign Biosynthesis," EPA/NSF Workshop on Green Syntheses and Processing in Chemical Manufacturing, Cincinnati, OH, July 12-13, 1994.

68. Chu, L., W.A. Zeltner, M.A. Anderson, "Microporous Alumino-Silicates Prepared by Sol-Gel Processing," American Ceramic society Meeting in the Symposium on Science, Technology, and Applications of Colloidal Suspensions, 1994.

69. Crittenden, J.C., Rudd, D.F, "Pollution Prevention Research Needs and the Role of Environmental Engineers in P2", Association of Environmental Engineering Professors/National Science Foundation Research Opportunities Workshop, Ann Arbor, MI, September 21, 1993.

70. Crittenden, J.C., Y. Zhang, D.W. Hand, R.P.S. Suri, J. Liu, D.L. Perram, E.G. Klun, S. Notthakun, and M.E. Mullins, "Photocatalytic Decontamination of Water," Florida Environmental Conference, Palm Coast, FL, October 19, 1992.

71. Crittenden, J.C., Y. Zhang, D.W. Hand, R.P.S. Suri, J. Liu, D.L. Perram, E.G. Klun, S. Notthakun, and M.E. Mullins, "Photocatalytic Decontamination of Water," Gordon Conference, New Hampton, NH, June 13-18, 1993.

72. Crittenden, J.C., Y. Zhang, D.W. Hand, R.P.S. Suri, J. Liu, D.L. Perram, E.G. Klun, S. Notthakun, and M.E. Mullins, "Photocatalytic Decontamination of Water," Hazardous Waste Conference, Notre Dame, IN, August 1992.

73. Crittenden, J.C., Y. Zhang, D.W. Hand, R.P.S. Suri, J. Liu, D.L. Perram, E.G. Klun, S. Notthakun, and M.E. Mullins, "Photocatalytic Decontamination of Water," Michigan Environmental Technology Innovation Conference, E. Lansing, MI, September, 1992.

74. Crittenden, J.C., Y. Zhang, D.W. Hand, R.P.S. Suri, J. Liu, D.L. Perram, E.G. Klun, S. Notthakun, and M.E. Mullins, "Photocatalytic Decontamination of Water," Seminar, Johnson Space Center, Houston, TX, October 1992.

75. Crittenden, J.C., Y. Zhang, D.W. Hand, R.P.S. Suri, J. Liu, D.L. Perram, E.G. Klun, S. Notthakun, and M.E. Mullins, "Photocatalytic Decontamination of Water," USEPA Risk Reduction Engineering Laboratory Workshop on Process Simulation and Optimization with Environmental Considerations, Cincinnati, OH, December 1992.

76. Crittenden, J. C., Y. Zhang, D.W. Hand, D.L. Perram, "Solar Detoxification of Groundwater Using Fixed-Bed Photocatalysts" Will be presented at ASME/JSME/JSES International Solar Energy Conference, Lahaina, Maui, Hawaii, March 1995.

77. Dewey, G. R., M.A. Kayser, L.L. Sutter, "Characterization of Electric Utility Coal Fly Ash for Use in Portland Cement Concrete," The American Power Conference, Chicago, IL, April 15,1994.

78. Dewey, G. R., M.L. Movrich, M.T. Cousino, "Municipal Solid Waste Incinerator Bottom Ash as an Aggregate Substitute in Hot-Mix Bituminous Mixtures," FHWA/EPA Symposium on Recovery and Effective Reuse of Discarded Materials and Byproducts for Construction of Highway Facilities, Denver, CO, October 19-22, 1993.

79. Eisele, T.C., and S.K. Kawatra, "Dewatering of Fine Particulates from Dilute Silicone Waste Dispersions," submitted for Presentation at the Second International Symposium on Metallurgical Processes for the Year 2000 and Beyond, TMS fall meeting, San Diego, CA, September 21-23, 1994.

80. Gulliver, J.S., B.T. Oakley, and M.J. Semmens, "A New In-Stream Aerator, " Hydraulic Engineering '93, Hydraulics Division, ASCE, San Francisco, CA, July 25-30, 1993.

81. Hand, D.W., J.C. Crittenden, J. Liu, S. Notthakun and D.L. Perram, "Destruction of Organic Pollutants Using Photoassisted Heterogeneous Catalytic Oxidation," The Advanced Oxidation Process Workshop sponsored by IWSA and AWWA held in Coral Gables, FL, April 13-14, 1992.

82. Hand, D.W., J.C. Crittenden, Y. Zhang, and E.G. Klun, "Photocatalytic Decontamination of Water Using Sunlight and TiO2 Impregnated Adsorbent and Non-adsorbent Supports," presented at The First International Conference on TiO2 Photocatalytic Purification and Treatment of Water and Air on November 8-13, 1992.

83. Hertz, D.W., P.P. Radecki, "Status Report on the Clean Process Advisory SystemTM: New Process Design Tools for Environmental Sustainability," Presented at 1994 AIChE Summer National Meeting, Pollution Prevention Topical Conference, Pollution Prevention Research: Collaborative Efforts Between Industry and Academia, Denver, CO, August 14-17, 1994.

84. Jewel, L.J., M.J. Semmens, "Solvent Recovery Using Hollow Fiber Membranes," ASCE National Conference on Environmental Engineering, Critical Issues in Water and Wastewater, Boulder, CO, July 14, 1994.

85. Johnson, D., M.J. Semmens, C.J. Gantzer, "Minimizing VOC and Odor Emissions through Controlled Oxygen Dissolution," Purdue Industrial Waste Conference, May, 1994.

86. Johnson, D., M.J. Semmens, C.J. Gantzer, "The Performance of a Low Head Oxygenator" American Fisheries Society National Conference, Halifax, Nova Scotia, August 22-25, 1994.

87. Johnson, D., M.J. Semmens, "The Performance of Unconfined Hollow Fiber Membranes as Pipe Flow and Mixed Flow Aerators," ASCE National Conference on Environmental Engineering, Critical Issues in Water and Wastewater, Boulder, CO, July 14, 1994.

88. Kim, N.K., D. Caspary, "Unit Operations Laboratory Experiments with a Total Distributed Control System," Presented at the 1993 International Scientists and Engineers Conference, Seoul, Korea, July, 1993.

89. Liu, J., D.W. Hand, J.C. Crittenden, D.L. Perram, and D. Hokanson, "Destruction of Toxic Organics Using Adsorption and Photocatalytic Regeneration," Poster Session held at the Annual AWWA Conference in Vancouver, B.C., Canada, June 18-25, 1992.

90. Maier, W., "Process Optimization of Biofiltration for Air Purification," Accepted for presentation, Third International Symposium: In-situ and On-Site Bioreclamation, San Diego, CA.

91. Mullins, M.E., "Environmental Considerations in Process Design and Simulation", Presentation contained within this workshop report prepared by Jack Eisenhauer and Shawna McQueen, EPA/DOE/AIChE Workshop, Cincinnati, OH, December 8-9, 1992.

92. Mullins, M.E., T.N. Rogers, "Physical Property Data Needs in Clean Manufacturing Designs," 207th American Chemical Society National Meeting, San Diego, CA, March, 1994.

93. Mullins, M.E., T.N. Rogers, "Physical Property Data Needs in Clean Manufacturing Designs," Symposium on Catalytic Reaction Engineering for Environmentally Benign Processes, ACS, San Diego, CA, April 3-8, 1994.

94. Nesbitt, C.C., "Environmentally-benign Materials and Processes," chaired session at Workshop for on Innovation in Materials Processing and Manufacture: Exploratory Concepts for Energy Applications," Oak Ridge, TN, June, 1993.

95. Nesbitt, C.C., S. Xue., "Recycling of Base Metals from Metal Wastes of Brass Foundries," Accepted for presentation at the International Symposium on Treatment and Minimization of Heavy Metal Containing Waste (1995 TMS Annual Meeting, Las Vegas, NV)

96. Niezyniccki, G.M., M.A. Anderson, C.G. Hill, Jr., "Separation of Gaseous Mixtures for Nanofiltration," Third International Conference on Inorganic Membranes, 1994.

97. Olson, W.W., "Environmentally Conscious Design and Manufacturing," Japan-USA Symposium on Flexible Automation, Kobe, Japan, July 11-18, 1994.

98. Olson, W.W., "Environmentally Conscious Design and Manufacturing," Yueng Nam University, Taegu, Korea, July 7, 1994.

99. Olson, W.W., "Environmentally Conscious Design and Manufacturing," Korean Advanced Institute of Science and Technology, Taejon, Korea, July 8, 1994.

100. Peterson, R.A., C.G. Hill, Jr., M.A. Anderson, "Development of Ceramic Membranes for Nanofiltration," Annual Meeting, American Filtration Society, 1993.

101. Radecki, P.P. et al, "Development of CPASTM: A Pollution Prevention Conceptual Process Design System," ACS Meeting, San Diego, CA, March 1994.

102. Radecki, P.P., D.W. Hertz, "Pollution Prevention Verification Through the Clean Process Advisory SystemTM," Presented before the Division of Environmental Chemistry, American Chemical Society, Washington, D.C., August 21-25, 1994.

103. Radecki, P.P., C.R. Baillod, J.C. Crittenden, J.T. Quigley, "Development of Industry/University/Government Collaborations by the Center for Clean Industrial and Treatment Technologies (CenCITT)", Presented at 1994 AIChE Summer National Meeting, Pollution Prevention Topical Conference, Denver, CO, August 14-17, 1994.

104. Radecki, P.P., "Computer-Based Methods for finding Green Synthesis Pathways and Industrial Processes for Manufacturing Chemicals," EPA-NSF Workshop on Green Syntheses and Processing in Chemical Manufacturing, Cincinnati, OH, July 12-13, 1994.

105. Rogers, T.N., M.E. Mullins, "A Revised UNIFAC Parameter Set for Estimating Henry`s Law Constants, and Solubilities," 1993 Midwest Thermodynamics Symposium, Michigan Technological University, May 1993.

106. Suri, R.P.S., J. Liu, D.W. Hand, J.C. Crittenden, D.L. Perram, Y. Zhang, D.R. Hokanson, and M.E. Mullins, "Destruction of Organic Compounds in Water Employing Heterogeneous Photocatalysis, " Poster Session, National AWWA Annual Conference, Vancouver, B.C., Canada, June 18-25, 1992.

107. Suri, R.P.S., J. Liu, D.W. Hand, J.C. Crittenden, D.L. Perram, Y. Zhang, D.R. Hokanson, and M.E. Mullins, "Destruction of Organic Compounds in Water Employing Heterogeneous Photocatalysis," Poster Session, Gordon Research Conference, Environmental Sciences, Redox Processes in Environmental Sciences, New Hampton, NH, June 1992.

108. Suri, R.P.S., Y. Zhang, Liu, J. C. Crittenden, D. W. Hand, D. L. Perram, "Heterogeneous Photocatalytic Oxidation of Hazardous Organic Contaminants in Water," Water Environment Federation 66th Annual Conference, Anaheim, CA, October 1993.

109. Suri, R.P.S. Y. Zhang, J. C. Crittenden, D. W. Hand, and D. L. Perram, "Innovative and Clean Industrial Treatment Technologies," Presented at the 1993 Michigan Water Environment Federation Annual Conference, Boyne Highlands, MI, June 1993.

110. Webster, E.T., C.G. Hill, Jr., M.A. Anderson, "A New Sol-Gel Process for Fabrication of Supported Ceramic Membranes," AIChE meeting, 1993.

111. Webster, E.T., M.A. Anderson, C.G. Hill, Jr., "Formation of defects in Ceramic Membranes Related to Conditions Employed During Fabrication," Third International Conference on Inorganic Membranes, 1994.

112. Wildman, D.L., R.A. Peterson, M.A. Anderson, C.G. Hill, Jr., "Investigation of Titania Membranes for Nanofiltration," Third International Conference on Inorganic Membranes, 1994.

113. Yaluris, G., R. J. Madon, L. M. Aparicio and J. A. Dumesic, "Microkinetic Analyses of Isoparaffin Reactions on Y-zeolites," 13th North American Meeting of the Catalysis Society, Pittsburgh, May 1993.

114. Yaluris, G., R.J. Madon, D.F. Rudd, J.A. Dumesic, "Catalytic Cycles and Selectivity of Hydrocarbon Cracking on Y-zeolite-based Catalysts," Presented at the Symposium on Catalytic Reaction Engineering for Environmentally Benign Processes at the San Diego ACS Meeting, March 13-18, 1994.

115. Yaluris, G., R.J. Madon, D.F. Rudd, J.A. Dumesic, "Catalytic Cycles and Selectivity of Hydrocarbon Cracking on Y-zeolite-based Catalysts," Presented at the Symposium on Catalytic Reaction Engineering for Environmentally Benign Processes, ACS, San Diego, CA, April 3-8, 1994.

116. Zeltner, W., M.A. Anderson, R. Peterson, "Synthesis and Characterization of Nanoparticle Alumino-silicate Materials in Their Use in Gas Phase Separations, and Fabrication of a Ceramic Membrane Module for Gas Phase Separations, American Ceramic Society, Indianapolis, IN, April 25-27.

117. Zhang, Y., J.C. Crittenden, D.W. Hand, D.L. Perram, "Solar Decontamination of Water with TiO2 Photocatalyst on Silica Based Supports" Presented at: American Water Works Association Annual Conference, San Antonio, TX, June 1993.

118. Zhang, Y., J.C. Crittenden, D.W. Hand, D.L. Perram, "Solar Detoxification of Groundwater Using Continuous Flow Reactor Packed with Supported Photocatalysts" Presented at 1994 Annual AIChE Meeting, San Francisco, CA, November 13-18, 1994.





TECHNOLOGY TRANSFER ACTIVITIES AND PRESENTATIONS: 6/92 - 8/94

Baillod, C.R. (lead), S.K. Kawatra, American Iron and Steel Institute Waste Recycle Technology Task Force, Pittsburgh, PA, June 12, 1992.

Baillod, C.R., Universities Council on Water Resources Annual Meeting, Charlottesville, VA, July 30, 1992.

Radecki, P.P., American Institute of Chemical Engineers Summer National Meeting, Minneapolis, MN, August 6-13, 1992.

Baillod, C.R., American Foundrymen's Society Environmental Affairs Conference, Dearborn, MI, August 17, 1992.

Radecki, P.P, Pollution Prevention in the Pulp and Paper Industry: International Symposium, Washington, D.C., August 17-21, 1992.

Radecki, P.P., Gearing Up Technology Transfer Event (Booth), Saginaw, MI, August 24, 1992

Crittenden, J.C., University of Notre Dame Hazardous Waste Conference, Notre Dame, IN, August 31, 1992.

Crittenden, J.C., Michigan Environmental Technology Innovation Conference, E. Lansing, MI, September 21, 1992

Tieder, R.E., Iron and Steel Industry Pollution Prevention Conference, Chicago, IL, October 14, 1992.

Crittenden, J.C., Florida Environmental Chemistry Conference, Palm Coast, FL, October 19, 1992.



Crittenden, J.C., Seminar-Johnson Space Center, Houston, TX, October 20, 1992.

Auer, M.T. (lead), International Symposium on Understanding Lake Superior through Research: Status and Prospects (Poster Session), Duluth, MN, November 8, 1992.

Radecki, P.P. (coord), CenCITT/Kohler Project Identification Workshop, Houghton, MI, November 30, 1992.

Tieder, R.E., Project Discussions and Negotiations: Foundry Association of Michigan, Environmental Services Division, Dow Corning, Western Michigan University, Technical Services Association, December 1-6, 1992.

Crittenden, J.C., M.E. Mullins, D.F. Rudd, USEPA Risk Reduction Engineering Lab Workshop on Process Simulation and Optimization with Environmental Considerations, Cincinnati, OH, December 8, 1992.

Radecki, P.P. (coord), Kohler Followup Plant Tour, Kohler, WI, January 22, 1993.

Radecki, P.P., Solvent Pulping Symposium, Technical Association of the Pulp and Paper Industry, February 2-3, 1993.

Hutzler, N.J., G. Dewey, Fort Howard Paper Company Research Needs Meeting, Green Bay, WI, March 2, 1993.

Nesbitt, C.C., ORNL Advanced Energy Projects Workshop on Innovation in Materials Processing and Manufacture: Exploratory Concepts for Energy Applications, Oak Ridge, TN, March, 11, 1993.

Radecki, P.P., ARPA Technology Reinvestment Project Unveiling, Detroit, MI, March 13, 1993.

Crittenden, J.C., P.P. Radecki, Design for the Environment Infrastructure Planning Meeting, Massachusetts Institute of Technology, Boston, MA, March 26, 1993

Radecki, P.P, White House Technology Reinvestment Project Briefing, April 1993.

Radecki, P.P. CenCITT Overview for USDOE Office of Technology Development Program Support Director (METAC Meeting), Ann Arbor, MI, April 28, 1993

Radecki, P.P., T. Co, N.K. Kim, D. Hubbard, B.A. Barna, CenCITT Overview at MTU Chemical Engineering Department Process Simulation and Control Center Industrial Advisory Board Meeting, Houghton, MI, May 20, 1993

Anderson, M.A., J.C. Crittenden, P.P. Radecki, DuPont/CenCITT Research Collaboration Identification Conference, Wilmington, DE, June 25, 1993

Suri, R.P.S., Michigan Water Environment Association Annual Conference, Harbor Springs, MI, June 27-30, 1993.

Radecki, P.P., USEPA Workshop on Identifying a Framework for the Future of Human Health and Environmental Risk Ranking, Washington, D.C., June 30, 1993

Radecki, P.P., T.N. Rogers, M.E. Mullins, Data Interfacing Needs at AIChE-DIPPR Project 911/912 Mid-Year Meeting, Houghton, MI, July 15, 1993

Crittenden, J.C., University of Michigan Transportation Research Institute / MDOT / MTU Funding Opportunities Meeting, Houghton, MI, July 22, 1993

Crittenden, J.C., D.F. Rudd, C.R. Baillod, A.S. Mayer, P.P. Radecki, Fourth Association of Environmental Engineering Professors Research Conference (in relation to ongoing research with CenCITT), Ann Arbor, MI, September 20-23, 1993.

Crittenden, J.C., P.P. Radecki, National Center for Manufacturing Sciences research collaboration discussion, Ann Arbor, MI, September 20-23, 1993.

Crittenden, J.C., Radecki, P.P Seminar at EPA Risk Reduction Engineering Laboratory, October 12-14, 1993.

Radecki, P.P. Research Needs Workshop for Identifying Economic Instruments to Promote Zero Discharge in the Lake Superior Basin, Houghton, MI, November 9-10, 1993.

Sandell, J.F., L. Sutter, J. Willemin, K. Ragland, Materials Processing Pollution Prevention Group concept paper and Collaborative research meeting, and Olmsted County Public Works, November 15, 1993.

Radecki, P.P., C.R. Szydlik, "QA/QC from Proposal to Publication" graduate student seminar, also Michigan Clean Technology Needs Survey Results presentation to CenCITT researchers, University of Minnesota (November 29-30, 1993); University of Wisconsin (December 1-2, 1993); Michigan Technological University (November 14, December 17, 1993).

Radecki, P.P, Michigan Industries Clean Technologies Discussions, MERRA State Environmental Roundtable, Ann Arbor, MI, December 7, 1993.



Radecki, P.P., "CPAS System Planning and CenCITT Overview", AIChE-CWRT CPAS Meeting (represented were The M.W. Kellogg Company, CH2M Hill, Bechtel, ENSR, Dow Chemical, AEA Technologies and Electric Power Research Institute), Houston, TX, February 10-11, 1994.

Barna, B.A., "An Economic Evaluation Tool for Use in the Pollution Prevention Conceptual Process Design Simulator," AIChE-CWRT CPAS Meeting, Houston, TX, February 10-11, 1994.

Rogers, T.N., "Physical Property Prediction for CPAS", AIChE-CWRT CPAS Meeting, Houston, TX, February 10-11, 1994.

Baillod, C.R., N.J. Hutzler, Wisconsin Electric Power, research needs discussion, February 15, 1994.

Baillod, C.R., P.P Radecki, introduction of CenCITT research programs to John R. Wyma, Legislative Director for Bart Stupak (US Representative from Michigan's 1st Congressional District) on February 21, 1994.

Hand, D.W., J.C. Crittenden, P.P. Radecki, EPA-RREL research symposium and panel discussion, Cincinnati, OH, March 15-17, 1994.

Radecki, P.P., M.H. Durfee, presentation on development of a multiuniversity Cooperative Outreach for Lake Economy and Technology Studies and a Modelling Group for Lake Superior, Binational Forum Meeting, Duluth, MN, March 22, 1994.

Radecki, P.P. CenCITT research programs presented to the National Center for Manufacturing Science's Environmentally Conscious Manufacturing's Strategic Initiative Group meeting, Dearborn, MI, March 31, 1994.

D.F. Rudd, Symposium on Catalytic Reaction Engineering for Environmentally Benign Processes, ACS, San Diego, CA, April 3-8, 1994.

Mullins,M.E. and P.P. Radecki, press conference on data and design tool needs for development of green synthesis pathways, ACS, San Diego, CA, April 3-8, 1994.

Radecki, P.P, "Introduction to CenCITT", Center for Waste Reduction Technologies Technology Transfer Committee Meeting, Atlanta, GA, April 17-20, 1994

Crittenden, J.C., American Energy Technology Company in Green Cove Springs, FL, April 19, 1994.

Crittenden, J.C., D.W. Hand, at Rohm and Haas to discuss the steam regeneration work, May 6, 1994.

Tieder, R.E., US Cast Metals Advisory Board June 2-3, 1994

Hertz, D.W., P.P. Radecki, "Overview of CenCITT University/Industry Cooperative Projects", Office of Industrial Technologies Industrial Waste Program of the Department of Energy, Washington, D.C.. June 9, 1994.

Radecki, P.P., D.W. Hertz, "Overview of CenCITT University/Industry Sustainable Development-Related Projects", Senior Policy Advisory to the U.S. Secretary of Commerce, Washington, D.C., June 9, 1994.

Cameron, D.C., P.P. Radecki, EPA Workshop on Green Synthesis and Processing in Chemical Manufacturing, Cincinnati, OH, July 13, 1994.

Crittenden, J.C., D.W. Hand, P.P. Radecki, D.R. Hokanson, F. Gobin, Meeting with Eiji Nishihara (Nishihara Corp), and Takashi Asano (UC-Davis), at MTU for CenCITT introduction, photocatalytic research discussion, and CPAS (Clean Process Advisory System), August 10, 1994.

Radecki, P.P., "Status Report on CenCITT CPAS Activities", Center for Waste Reduction Technologies Technology Transfer Committee Meeting, Denver, CO, August 13, 1994.

Radecki, P.P., "Development of Industry/University/Government Collaborations by the Center for Clean Industrial and Treatment Technologies (CenCITT)", Presented at 1994 AIChE Summer National Meeting, Pollution Prevention Topical Conference, Denver, CO, August 14-17, 1994.



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