Pilot
Study "Clean Products
   and Processes"
     Phase II
Annual Report
 sponsored by
  hosted by

                             Cefraro ^CS; - /fa/y, f 1 - 15 May 2003

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                ITM-CNR
        Presentations
        ^^^^^^M
           Participants
       Final Remarks
2004
                   Country
                                          1stNATO/CCMS Pilot Study "Clean Products and Processes" - Phase II
                                                                                        Introduction
The Council of the North Atlantic Treaty Organization (NATO) established in 1969 the Committee on
the Challenges to  Modern Society  (CCMS) with the  aim  to create  a network of Countries for
exchanging  information, ideas, knowledge, technologies  on topics  of interest for  the Society.  In
particular, the achievement of a sustainable growth is one of the issues that the CCMS Pilot Study on
Clean Products and Processes considers as really important for the next future: in order to produce "in
harmony" with  the environment, while  successfully  competing,  industries  need  cleaner and
economically attractive technologies. The series of meetings held during the  Phase I of the Pilot Study
had the positive fallout of the creation of  an international infrastructure which  actively  shared
expertises in cleaner processes.  The Phase II, which is  in  progress, will focus on increasing the
collaboration among  countries in solving common  problems  and on in-depth discussions and
assessments in the already identified industry sectors of importance.
The NATO Committee on the Challenges to Modern Society (CCMS) has  sponsored until now five
Pilot Study meetings on Clean Products and Processes - Phase I:
*  the first meeting was held in Cincinnati, Ohio, USA, in 1998;
*  the second meeting in Belfast,  Northern Ireland, in 1999;
*  the third meeting in Copenhagen, Denmark, in 2000;
*  the forth meeting in Oviedo, Spain, in 2001;
*  the fifth and concluding meeting in Vilnius, Lithuania, in 2002.
The five years of activity have been  very useful  for creating the infrastructure  for  the Pilot Study
network; five more years of Phase II have been approuved (November 2002-October 2007).
The meeting held in Calabria, Italy, on May 2003, was the first meeting of the NATO/CCMS Pilot Study
on Clean Products and Processes-Phase II. It was hosted by the Institute on Membrane Technology,
ITM-CNR, Rende (CS), Italy.
Its object was the discussion about the progresses made worldwide in developing clean technologies
in the logic of the sustainable growth. The aim of the meeting was the exchange of experience among
all countries involved on problems related to the environmental impact of industrial productions.
Techniques  and methodologies developed for improving the performance of existing productive cycles
and/or for defining new cleaner systems  of productions were illustrated. The share of the knowledge
would help in reaching possible solutions  to specific problems, especially among countries with similar
environmental impact.
Cetraro (CS) - Italy, 11-15 May '03

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                              1stNATO/CCMS Pilot Study "Clean Products and Processes" - Phase II
           ITM-CNR
        Introduction
        Participants
        ^^^^^M
     Final Remarks
     ^^^^^^^^
   2004 Host Country
             CD
                                                          Sunday, May 11, 2003
                             >  A Review on the Membrane Research Activities in Ital
   Enrico Drioli
">  Overview of the Meetinc Acenda. Technical Proeram and Tours
                               Daniel Mwrau
                            <* Renort on 2002 Meetinc
   Jurats Staniskis
<*  Selection and Use of Environmental Indicators in Different
   NATO Member States
   Horst Pohle
<*  Life Cvcle TlmDact^ Assessment
   David Pennine/ton
 >  Sustainabilitv Indicators and ReDortinc Mechanisms in
                               Euronean Recions
  Annik Fet
<* Environmental Manacement Accountinc TEMA1
                               Gyula Zilahy
                            <* TRACI-Tool for the Reduction and Assessment of Chemical and
                               other Environmental ImDacts
                               Dan Murra
Cetraro (CS) - Italy, 11-15 May '03

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     fP") ITM-CNR
     •J
                               1stNATO/CCMS Pilot Study "Clean Products and Processes" - Phase II
                                                       Monday, May 13, 2003
        Introduction
        Participants
     Final Remarks
    ^^^^^^^M
   2004 Host Country
    ^^^^^^^M
             CD Info
                               <* Desien and Simulation of Environmental Conscious Chemical
   Processes
                                 Teresa Mata
                               "> Bevond the Molecular Frontier: Challenees for Chemist
                                 and Chemical Encineerinr
   Tomas ChaDman
 >  Procramme on Sustainable Industrial DeveloDment in
   Lithuania
   Jurgis Staniskis
<*  Clean Products and Processes Undate - Universitv of Natal
   Chris Buckley
<*  Break-throuch of Water Reuse in Textile Industrv throuch
   Develonment of Generic Water Recvcle Schemes
                                 Henrik Wenzel
                               >  Ionic Liauid Research and ADDlication
                                 Jim Swindall
                               ~> Some Case Studies on Clean Products and Processes
                                 David Wolf. Chaim Foraacs
Cetraro (CS) - Italy, 11-15 May '03

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                                 1stNATO/CCMS Pilot Study "Clean Products and Processes" - Phase II
            ITM-CNR
         Introduction
         Participants


      Final Remarks
     ^^^^^^^^
   2004 Host Country
              ^^^M

              CD Info
                                                       Wednesday, May 14, 2003
                               Process Intensification in Euronean Union : Current Work and Future
                               Plans. Gioraos Gallios
                               Wettabilitv Determination as an Important Factor in Desien and
                               Environmental Performance of Some Industrial Processes. Andrzei
Doniec

DeveloDment and Inteeration of New Processes for Greenhouse Gases
                               Manaeement in Multi-Plant Chemical Production Comnlexes. Ralnh Pike
                               Studies on the Purification of Nonwater Media bv Ceramic Membranes.
                               Gueoraui G. Kaaramanov
Altenatives for the Senaration of Oreanic Acids as Exanroles of Process
Intensification. Jose Coca
Process Intensification bv Modeling and Modifvine Packed Bed
Reactor. Antonio Martins
New Technoloeies for Imnrovine Gas Liauid Transfer Processes and
Catalvtic Reactions. Alessandra Criscuoli
Rationalization of Productive Cvcles in the Aero-Food Industries bv
                               Innovative Processes. Alfredo Cassano
                               Slovak Bv-Droducts in Intensification of Wastewater Treatment
                               Processes. M. Vaclavikova
                               Reuse of Waste Materials from Zinc Industrv for SorDtion of Hvdroeen
                               Sulfide. AuselAtimtau
                               ExDerience with Cleaner Production in the Ledeko. Inc. Aericultural
                               Enterprise, Letovice, The Czech ReDublic. Frantisek Bozek
                               Establishine and Manaeine Waste Minimisation Clubs in South Africa.
                               Chris Buckley
                               Network of Excellence - TELES. Viorel Harceaa
                               Tonics for Cooneration
Cetraro (CS) - Italy, 11-15 May '03

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    fP") ITM-CNR
     •J
                            1stNATO/CCMS Pilot Study "Clean Products and Processes" - Phase II
                                              Thursday, May 15, 2003
        Introduction
        Participants


     Final Remarks
    ^^^^^^^^
  2004 Host Country
            ^^^M

            CD Info
                             Sustainable DeveloDment usine Macroeconomic and
Microeconomic Indicators
                             Peter Glavic
                              sroduction from \vaste brine.
Stefka Tevavitcharova and Christo Balarew
Chemical Disoersants and Bioremediation for the
Treatment of Oil Snills
Jose Coca
Cleaner Production Policv in context of Market
Economv& Sustainable DeveloDment  for Ukraine and
other countries of transition economv
                             William Zadorsku
                             Evaluation of the Proeress of the Pilot Studv and Onen
                             Discussion
                             Subhas Sikdar
                             Annual ReDort Presentation
                             Dan Murray

                             Discussion on Future Directions for the Pilot Stud
                             Dan Murran
                             Meetina Wrao U~~
                              Subhas Sikdar
Cetraro (CS) - Italy, 11-15 May '03

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                         1stNATO/CCMS Pilot Study "Clean Products and Processes" - Phase II
     Introduction
   Presentations
  Final Remarks
2004 Host Country
         CD Info

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      fP")  ITM-CNR
       •J
          Introduction
          ^^^^m
       Presentations
       ^^^^^^M
          Participants
   2004 Host Country
    ^^^^^^^M
                CD Info
                                     1stNATO/CCMS Pilot Study "Clean Products and Processes" - Phase II
                                          Final  Remarks
The 2003 NATO CCMS Meeting has been an useful opportunity to point out the common
interest among  participants on topic related  to  environmental  concerns.  It has been
characterized by intensive discussions in all the  presentations;  various suggestions for
further activities have been also presented.
Six topics for cooperation have been underlined during the five  days of Workshop, and
coordinators have been indicated:

           [1]   Sustainability metrics-reporting mechanisms
(Coordinator: Annik Magerholm Fet, Faculty of Social Sciences and Technology
Management, Department of Industrial Economics and Technology Management,
Norwegian University of Science and Technology, e-mail: fet@iot.ntnu.no)
           [2]   Train the trainers implement EMA
(Coordinator: Gyula Zilahy, Hungarian Cleaner Production Centre, Budapest University of
Economic Sciences and Public Administration, e-mail: zilahy@enviro.bke.hu)
           [3]   Education and training on sustainable production
(Coordinator: Peter Glavic, University of Maribor, Faculty of Chemistry and Chemical
Engineering, e-mail: glavic@uni-mb.si)
           [4]   Cleaner production policy in transition economy Countries
           (Coordinator: William Zadorsky, Ukrainian Ecological Academy of Sciences,
Ukrainian State University  of Chemical Engineering, e-mail: ecofond@ecofond.dp.ua)
           [5]   Indicators for potential new sustainable technologies
(Coordinator: Enrico Drioli, ITM - CNR at University of Calabria, e-mail: e.Drioli@itm.cnr.it)
           [6]   Waste minimization club
(Coordinator: Chris Buckley, Pollution Research Group, University of Natal, e-mail:
BUCKLEYOnu.ac.za)
Cetraro (CS) - Italy, 11-15 May '03

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     fP")  ITM-CNR
     •J
         Introduction
        ^^^^m
      Presentations
      ^^^^^^M
         Participants
   2004 Host Country
    ^^^^^^^M
             CD Info
                               1stNATO/CCMS Pilot Study "Clean Products and Processes" - Phase II
                                   Final Remarks
The possibility to organize specific projects to be carried out under the
umbrella  of  the  CCMS  Pilot  Study, with financial  sponsorship from
International Agencies or other organizations has been also analyzed.
Prof. Drioli suggested, in  particular, the  use of the  FP6 instruments for
elaborating specific joint projects on the topics of interest and the creation
of a roadmap of the FP6 projects (by ITM-CNR; Italy) suitable  for that
purpose.  Prof.  Drioli was asked  to  elaborate  a short  report  on the
opportunities existing in the FP6 of the European Union.
During the meeting  technical visits to  industrial sites of the region were
organized and in particular to:

1.          Amarelli Liquorice
C/da Amarelli S.S. 106 - 87068 Rossano Scale CS (Italy)
tel.+39/0983511219-fax+39/0983510512
 11 m iij 111 (• >J I iisTi» CsTl fc I lIsR HlTsl I
                                      OS AS agro-foods
                           Contrada Ciparsia
                           87012Castrovillari(CS)
                           tel 0981 - 480960 , fax 0981 - 480903
                           3.          Mediterranea R.&S.
                           Mediterranea R.& S.
                           C/da Coretto
                           87046 Montalto Uffugo CS
                           4.          GIAS
                           Gruppo Industrial Alimenti Surgelati - Mongrassano
Cetraro (CS) - Italy, 11-15 May '03

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         ITM-CNR
  Introduction
  ^^^^m
Presentations
       Participants
    Final Remarks
           CD Info
                         1stNATO/CCMS Pilot Study "Clean Products and Processes" - Phase II
                                           2OO4 Host Countr
                      At the end of the Workshop the host Country for the 2004 meeting has been chosen:

                           Hungary/

                          JK^^^KiB
Cetraro rCS) - Jta//, 11-15 May '03

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              ITM-CNR
                                     1stNATO/CCMS Pilot Study "Clean Products and Processes" - Phase II
                                                                 Notice
          Introduction
          ^^^^m
       Presentations
      ^^^^^^^m
          Participants
      Final Remarks
      ^^^^^^^^
   2004 Host Country
This report was prepared under the auspices of the North Atlantic Treaty
Organization's Committee on the Challenges of Modern Society (NATO/CCMS)
as a service to the technical community by the United States Environmental
Protection Agency (U.S. EPA) and the Institute of Membrane Technology at the
University of Calabria, Italy. The views expressed in these proceedings are
those of the individual authors and od not necessarily reflect the views and
policies of the U.S. EPA. Scientists in EPA's Office of Research and
Development have prepared the EPA sections, and those sections have been
reviewed in accordance with EPA's peer and administrative review policies and
approved for presentation and publication. This report was produced as a result
of a cooperative agreement with U.S. EPA's National Risk Management
Research  Laboratory (NRMRL) and the Institute of Membrane Technology (ITM)
at the University of Calabria, Italy. This report was produced and edited by Dr.
Maria A. Liberti, ITM, and reviewed by Mr. Daniel J. Murray and Dr. Subhas K.
Sikdar of NRMRL. Mention of trade names or specific applications does not
imply endorsement or acceptance by U.S. EPA or the University of Calabria.
                                                                                      EPA/625/C-03/009
                                                                                      NATO Report Number 266
                                                                                      December 2003
                                                                                      www.nato.int/ccms
Cetraro (CS) - Italy, 11-15 May '03

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 ITM - CNR
I Istituto per la Tecnologia delle Membrane i
   A Review on the Membrane
    Research Activities in Italy
               Prof. Enrico Drioli

        Research Institute on Membrane Technology, c/o
          University of Calabria, Via P. Bucci, cubo 17/c,
                   Rende (CS), Italy

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 ITM-CNR Membrane Science and Technology
I Istituto per 13 1 ecnologia delle Membrane ,
             Reaction
            Engineering
Material
Processing
 ITM
Rende
M
                     Membrane
                     Engineering
          Padova
            Process
            Technology

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  ITM - CNR
Membrane  Science
I Istituto per 13 1 ecnologia delle Membrane ,
                              Transport
                              Phenomena
                Colloid and
                Interface
                Chemistry
                  Polymer
                  Chemistry
                              Membrane
                               Science
                 m dynamics
               lectrochemis
                    Process
                   Dynamics
                               Physical
                              Chemistry

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   ITM - CNR  Institute for  Membrane Technology
  I Istituto per la Tecnologia delle Membrane i
Section Rende
c/o Universita della Calabria
ViaPietro Bucci, cubo!7/C,
87030 Rende, Italy
Tel.:0984 492039/402706
Fax.:0984 402103
E-mail: e.drioliftfUtm.cs.cnr.it
Section Padova
c/o Dipartimento di chimica
organica. Universita di Padova
Via Francesco Marzolo 1,
35131 Padova, Italy
Tel.:0498 275261/8275253
Fax.:0498275239
E-mail:
gianfranco.scorrano@unipd.it
Director
Permanent researchers
Other staff
PhD students
Contracts, scholarships
Others

Responsible
Scorrano
Permanent researchers
Other staff
PhD students
Contracts, scholarships
Others
Prof. Enrico Drioli
xxx
xxx
xxx
xxx
xxx

Prof. Gianfranco

xxx
xxx
xxx
xxx
xxx

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 ITM - CNR  Institute on Membrane Technology
I Istituto per la Tecnologia delle Membrane i
>  The Institute on Membrane Technology (ITM-CNR) is
   a structure created by the National Research Centre of
   Italy (CNR - Consiglio Nazionale delle Ricerche) for the
   development, at national and international level, of
   membrane science and technology.
>  The Institute is located in the existing structure of the
   University of Calabria, Rende (Cosenza), and has a
   section located at the University of Padova (which is
   involved in the synthesis of new materials to be used in the
   preparation of membranes).

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  ITM - CNR
Personnel
I Istituto per la Tecnologia delle Membrane i
>  The Institute has 28 units of permanent staff and about
   30 temporary units constituted by visiting professors,
   researchers, Ph.D. students, post-doctoral fellowships,
   high-educational fellowships from national and
   international Institutions.
>  It is a multidisciplinary Institute based on backgrounds
   in chemical engineering; process engineering; chemistry
   (organic and physical); biological science; food science;
   material science and physics.

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 ITM - CNR
Collaborations
I Istituto per la Tecnologia delle Membrane i
  A significant exchange of young researchers,
  e.g. with Spain, France, Holland, Slovakia,
  Poland, Russia, Algeria, Argentina, South Korea,
  China, Japan, USA, is strongly encouraged to
  integrate research activities at international
  level.
> Formal bilateral and multilateral agreements
  with Japan, South Korea, China, Russia, France,
  Marocco, and Egypt have been approved.

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  ITM - CNR
Research activities
 I Istituto per la Tecnologia delle Membrane i
> The activity of the Institute is focused on the research and
  development of membrane science and technology. The
  main research activities are related to the following topics:
 1  Catalytic membranes and catalytic membrane
    reactors;
 2  Integrated membrane operations;
 3  Membrane distillation and membrane contactors;
 4  Membrane preparation and characterisation;
 5  Fundamental studies of transport phenomena in
    organic and inorganic membranes.
 6  Polymeric membranes for artificial organs

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 ITM - CNR        Examples of research topics
I Istituto per la Tecnologia delle Membrane i
   Catalytic membranes and catalytic membrane reactors
    - Inorganic membranes,
        •  e.g. steam reforming, partial oxidation of methane to syngas
    - Biocatalytic membranes
        •  e.g. enzyme membrane reactions, continuous membrane
          fermentations, enantioselective membranes

   Integrated membrane operations. Integration of classical
   engineering processes with membrane separation
   technology
    - Wastewater treatment and product recovery in leather industry
    - Production of fruit juices
    - Etc..

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 ITM - CNR     Examples of research topics (2)
I Istituto per la Tecnologia delle Membrane i
   Membranes as artificial organs
   Membrane distillation and membrane contactors
    - Potable water production from seawater and brackish water
    - Water/alcohol separations
    - Purification of physiological solutions
    - Preparation of water with controlled gas composition

   Transport phenomena in organic, inorganic and hybrid
   membranes
    - Experimental study of fundamental aspects of mass transport in
      relation to membrane preparation and membrane structure.
    - Theoretical support by molecular dynamics simulations.

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  ITM - CNR  Research activities of Padova section
I Istituto per la Tecnologia delle Membrane i
1  Understanding transport phenomena through membranes by
   theoretical studies of weak intermolecular interactions
2  Catalytic membranes and degradation of organic pollutants
3  Polymeric membranes incorporating fullerenes and
   nanotubes
4  Transition metal complexes in membrane-mimetic systems
5  Supramolecular chemistry. Reactivity and molecular
   recognition in micelles, vesicular aggregates and polymeric
   membranes

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 ITM - CNR
I Istituto per 13 1 ecnologia delle Membrane ,
           Some new technologies
                Membrane contactors
               Membrane crystallizers
             Emulsion membrane reactors

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 ITM - CNR
I Istituto per 13 1 ecnologia delle Membrane ,
    Selection of collaboration projects
                oflTM-CNR
                   Brite-Euraml
                     Grace
                    PERMOD
                     Murst
                 INCO-Copernicus

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 ITM - CNR
I Istituto per 13 1 ecnologia delle Membrane ,
    Research activities on membranes
     in academic institutes in Italy

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 ITM - CNR
Academic research activities
I Istituto per la Tecnologia delle Membrane i
   University of Calabria
    - see also ITM-CNR

   University of Turin
    - Polymers for membrane formation, synthesis and applications
    - Molecular imprinting polymers
    - Inverse phase transfer catalysis
    - Bioremediation of waste water

   Polytechnic  of Milan
    - Material properties and transport phenomena of membranes

   University of Perugia
    - Inorganic and protonic membranes for fuel cells

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 ITM - CNR    Academic research activities (2)
I Istituto per la Tecnologia delle Membrane i
  University of Genua
   -  UF, MF, RO, PV, Membrane reactors
   -  Wastewater treatment
  University of Bologna
   -  Membrane separations and diffusion in polymers
   -  Thermodynamics and thermomechanical properties of
      polymeric fluids
   -  Chemical processes in microelectronics
   -  Catalytic membranes and kinetics of heterogeneous
      processes
   -  Membrane distillation
   -  Pervaporation
  University of Palermo
   -  Anodic ceramic membranes

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 ITM - CNR
I Istituto per 13 1 ecnologia delle Membrane ,
    Membrane processes and research
     activities in the Italian industry

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 ITM - CNR
Industrial membrane activities
I Istituto per la Tecnologia delle Membrane i
  Membrane activities in the Italian industry concern both
  application and research, and are currently experiencing a
  strong growth.

  Typical examples are in food and dairy industry, energy
  conversion, (waste)water treatment, electrochemical
  applications, integrated processes et cetera.

  Many R&D projects are carried out in close collaboration
  with other research institutes and are financed by the
  European Union and national government.

  There is no more industrial production of new membranes
  in Italy

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  ITM - CNR
Membrane and material manufacture
I Istituto per la Tecnologia delle Membrane i
   Belco SpA
   FilterPar Sri
   Millipore SpA
   Italy)
   Permacare
   Separem
       Biomedical applications
       Water treatment (UF, MF)
       Pure and ultrapure water (sales in

       Water treatment (RO, NF, UF, MF)
       Impermeable and breathable tissues
Raw material production
•  Ausimont       - Production of fluorinated polymers

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 ITM - CNR
Water and wastewater treatment
I Istituto per la Tecnologia delle Membrane i
   Purification, demineralisation, Ind. effluent recycling
    - Bono Sistemi SpA

   Equipment manufacture
    - Culligan Italiana              - FDT Sri
    - Hydro air research             - Hytek Sri

   Water purification, pyrogene-free steam production
    -  Stilmas SpA

   Technology development
    - Tecnomil

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 ITM - CNR      Special membrane processes
I Istituto per la Tecnologia delle Membrane i
  Impianti Elettrochimici O. De Nora
   -  Chlor alkali plants to produce chlorine, caustic soda,
      caustic potash, and downstream derivatives such as
      hydrochloric acid and sodium hypochlorite.
   -  Materials and services for mercury and diaphragm
      chlor-alkali plants and their revamping and upgrading.

  Tecno Project Industriale
   -  Treatment of air and industrial gases
   -  CO2 production and recovery

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 ITM - CNR   Miscellaneous membrane operations
I Istituto per la Tecnologia delle Membrane i
  Purification of pharmaceutical products & intermediates
   -  Bracco SpA

  Filtration and filtration equipment manufacture
   -  Diemme Filter division

  Filtration, concentration, purification in pharmaceutical,
  chemical, biotechnological, food and beverage industry.
  Membrane processes and membrane unit production.
   -  Koch Membrane Systems
   -  Permeare Sri

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 ITM - CNR
I Istituto per 13 1 ecnologia delle Membrane ,
              Selected institutions

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 ITM - CNR
ENEA
I Istituto per la Tecnologia delle Membrane i
  The National Institute for Alternative Energy
  (ENEA) was founded to study the use of nuclear
  energy. With the decision of the Italian
  government to freeze the use of nuclear energy,
  ENEA has focussed on new energy sources and
  on new processes for energy conversion:

  Membrane and Membrane Reactor development
   - Metal membranes, Integrated systems separator/reactor

  Process development
   - Methanol partial oxidation, water gas shift reaction,
     hydrogen purification, fuel cells

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 ITM - CNR
De Nora Group
I Istituto per 13 1 ecnologia delle Membrane ,
   The De Nora Group was originally established to
   design, manufacture and install electrochemical
   plants, electrolyzers and electrodes.
                                         O GRUPPQ DE NORA
                                         • SUBSIDIARIES OF
                                        I., DE NORAELETTRODl

                                            \
                  WORLDWIDE ORGANIZATION

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     ITM - CNR  De Nora Group / Nuvera fuel cells
    I Istituto per 13 1 ecnologia delle Membrane ,
  Nuvera Fuel Cells, one of the joint
  ventures of the De Nora Group, is an
  international company based in Milan and
  Cambridge (USA), producing from small
  portable fuel cell units to large industrial
  power plants.
• Nuvera has extensive collaborations with
  ITM-CNR in the development of
  combustion cells and membrane reactors.
                               www.nuvera. com
                                          1 hW Hydrogen
                                          Power Module

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 ITM - CNR
I Istitlrto per 13 1 ecnologia deBe Membrane ,
Enel Green Power / ERGA
                                        Enel GreenPower
                                              CNR-ITM

                                  Membrane systems for the
                              treatment and valorization of gas
                             emissions from geothermal plants
                       PROPOSTA Dl RICERCA Al SENSI DM 593, Art. 5

    ' Enel GreenPower

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 ITM - CNR                     Enel GreenPower / CNR-ITM
I Istituto per la Tecnologia delle Membrane i
   Enel GreenPower: Firms controlled by Enel and finalized to the
 production of  renewable energy  (geothermal, mini-hydro,  wind,
 photovoltaic,  biomass, and biogas plants)
 Via Andrea Pisano, 120 - PISA
   CNR-ITM: Istituto per la Tecnologia delle Membrane
 c/o Universita della Calabria, Arcavacata di Rende (CS)

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ITM - CNR
Geothermic Energy Production
                                                      Waste gaseous
                                                      fraction emission
     15 MW
     (METTJ)   (MM,-ECC,,.)

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ITM - CNR
Enel GreenPower/ CNR-ITM



WASTE
GAS
i
1 1 1 1 1
C02 H2S CH4 H2 N2 O2,
95% 1% 1% 2% 1%


i
Ar, He, CO
traces
     Residual Geothermic Gas is regulated by the actual legislation as
             waste and it's subjected to a specific control
      Being able to transform this critical problem in an opportunity
      through the application of innovative technology of membrane
                  systems is the aim of this project.

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  ITM - CNR
              Aims
 I Istituto per 13 1 ecnologia delle Membrane ,
  GEOTHERMIC
  WASTE GAS
REDUCING TRADITIONAL
PLANTS SIZE
                                                  WASTE TREATMENT BY
                                                  BIOCATALYTIC MEMBRANE
                                                  REACTORS
Separation through membrane systems of gaseous components and
recovery of those commercially or energetically of interest (CO2, H2, CH4)
H2S separation from waste fluid: size reduction of traditional plants
H2S reduction through biocatalytic membrane reactors

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   ITM - CNR
            Enel GreenPower/ CNR-ITM
 I Istituto per la Tecnologia delle Membrane i
  H2S REDUCTION THROUGH BIOCATALYTIC MEMBRANE REACTORS
Geothermic gas
 COMMERCIALIZATION
                      Geothermic gas - H2S
                       SULFOBACTERIA
                           H2S04
ADDITION TO FLUIDS TO
    AVOID SILICA
   PRECIPITATION
H2S04+2NH3^(NH4)2S04
FERTILIZER

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    ITM - CNR
Advantages
   I Istituto per la Tecnologia delle Membrane i
=> SIDE PROCESS OF GAS COMMERCIALLY (CO2) AND ENERGETICALLY (H2, CH4)
OF INTEREST ASSOCIATED TO THE TRADITIONAL PROCESS OF GEOTHERMAL
PRODUCTION
  REALIZATION OF LOW BUDGET PROCESSES OF H2S SEPARATION AND
   POSSIBILITY OF EXPLOITING GEOTHERMIC RESERVOIR RECENTLY NOT in USE
 low entaloic fluids but rich in uncondensable aas)
   INNOVATIVE AND PATENTABLE KNOW-HOW (innovative use of membrane systems)

-------
 ITM - CNR
Tecnoalimenti
I Istituto per la Tecnologia delle Membrane i
  Tecnoalimenti is a non-profit organisation dedicated to
  promotion and execution of research programs in the food
  sector, in particular focussed on the small and medium
  enterprises. Activities further comprise feasibility and
  market studies, financial consultancy, implementation of
  quality systems, scientific publishing and organisation of
  conferences.
  Tecnoalimenti collaborates  with numerous other companies
  in the food sector and other institutes such as ITM-CNR
  A selection of the research projects involves waste water
  treatment, cheese production methods, recovery of useful
  products from wine production waste.

-------
 ITM - CNR  Food, beverage and dairy industry
I Istituto per la Tecnologia delle Membrane i
  Traditionally one of the strong industries in Italy.
  e.g. Parmalat has membrane based processes for,
  and corresponding research efforts in the field of:
   - production of calcium-enriched milk
   - milk  and  cream  concentration  for  production  of
     yoghurt and typical cheeses
   - production  of long-lasting  milk by  pasteurisation
     through membranes
   - production of clear fruit juices
   - demineralisation of water

-------
 ITM - CNR
Conclusions and outlook
I Istituto per la Tecnologia delle Membrane i
  Membrane research has a bright future in Italy. An
  increasing attention for a healthy environment, low energy
  consumption and increased product quality will promote
  the application of membrane based-processes.
  Considerable growth is expected in the traditionally strong
  industries, such as the food, beverage and dairy industry, and
  the leather and textile industry, which have a relatively high
  environmental impact.
  Among the many other promising sectors, also on a world-
  wide scale, are drinking water production and new processes
  for energy conversion (e.g. fuel cells).

-------
Clean Products and Processes
            Phase I
         Sixth Annual Meeting
            Cetraro, Italy
           Meeting Overview

        Dan Murray, Co-Director

-------
      Meeting Organizers
Professor Enrico Drioli
Ms. Alessandra Criscuoli
Ms. Mariella Liberti
      bhas Sikdar

-------
        Program Overview
Technical Program
 • Workshop on Environmental/Sustainability
  Indicators
 • Topical Symposium on Process Intensification
Field Trip/Industrial Visits
Special Events
Closina Session

-------
       Technical Program
Workshop on Environmental/Sustainability
Indicators
Pilot Project Updates
Delegate Open Forum
Topical Symposium on Process
Intensification
Tutorial on Setting Up Waste Minimization
"Clubs"

-------
     Field  Trip/Industrial Visits
    Amarelli Liquorice
    OSAS Agro-Foods
    Mediterranea R.&S.
        Altomonte
Church of Santa Maria della
       Consolazione
                                 daft 731
                                 L1QU1RIZ1A
non ancora disponibile
      I
                                       I

-------
           Special  Events
                            UNM-RSITA DELIA CALABRIA
Institute on
Membrane
Technology (ITM)
Rector of the
University of Calabria
Mayor of Cosenza City
Dinner in Old
Cosenza/Rende
CAMPUS CM JWGWGKTA

-------
         Closing Session
2002 Annual Report Presentation
Evaluation of Progress of Pilot Study
Topics and Focus for 2004 Meeting
Selection of Host Country and Dates for
2004 Annual Meeting
Meeting Wrap Up

-------
We'll Remember the Technical
      Presentations...
        k-
        a
 ift

-------
  the  Beautiful Sights
    ©Tony Poppa, 2001

F! if ii ii
fl B P .B II I!
                         5

-------

-------
    ...the Food and Drink...
v
-i

         1

-------

-------
...and the Friends and Colleagues!

                      r

                    OS(

-------
NATO CCMS Pilot Study on Cleaner Products and
    2002 5th Annual  Meeting
         Vilnius, Lithuania
            SUMMARY
          Prof. Jurgis K. STANISKIS
    The Institute of Environmental Engineering, Kaunas
      University of Technology, Kaunas, Lithuania


-------
             Technical data
Number of participants
46

Meeting with President of the Republic of Lithuania Valdas
  Adamkus at the Presidential Palace

-------
              Technical data
Countries

Germany, Czech Republic,
  Ukraine, Bulgaria, Poland,
  Italy, Sweden, Russia, UK,
  Spain, USA, Denmark,
  Portugal, Turkey, Norway,
  Hungary, Moldova,
  Slovenia, Lithuania
Representative
of UNEP


-------
             Technical data
Number of presentations

Number of Tour de Tabl
Presentations     10

-------
          Technical data
Visited companies:

1. JSC "Alytaus tekstil
            (textile)
2. JSC "Snaige"
    (refrigerator production)]
3. JSC "Alita"
    (wine and sparkling wine)


-------
                   Technical data

Special topic: Industrial Ecology
                        Arunas Kundrotas
                        Minister of
                        Lithuanian Ministry
                        of Environment
Prof. Lennart
Nielsen
Royal Stockholm
Technical Institute
(Sweden)

                        Nerijus Datkunas
                        Financial director
                        JSC "Utenos
                        trikotazas"
 Arunas
 Pasvenskas
 General director
 JSC "Klaipedos
 kartonas"

-------
       Selected  papers for the journal

 "Clean Technologies and Environmental
                          Policy"
1.   Huhtala A. "Strategies and Mechanisms to Promote Cleaner Production
    Financing"
2.   Staniskis J.K., Stasiskiene Z. "Cleaner Production Financing: Possibilities
    and Barriers"
3.   Staniskis J.K., Arbaciauskas V. "Industrial Ecology in University Curricula:
    New International MSc Programme in Cleaner Production and Environmental
    Management"
4.   Fet A. "Industrial Ecology and Eco-Efficiency. Introduction to the Concepts"
5.   Karlsson M. "Extended Producer Responsibility in Cleaner Production"
6.   Kruopiene J. "Chemicals Risk Management in Enterprises"


-------
Selection and Use of Environmental
Performance Indicators in different
        NATO Member Stat
   NATO CCMS Pilot Study on Clean Products and
         ^     Processes,    f    ^^_
            2003 annual meeting
            May 11 to 15, 2003
        Hotel San Michele, Cetraro, Italy

-------
An indicator depicts a detail of a
  complex phenomenon ...
   - the way an increased temperature
       indicates the condition of one
   physiological function, but not of the
           body as a whole-
 i

-------
Sustainable development is a complex
         phenomenon.
   Economy
         Environment

-------
Environmental Indicators  on
          different level
                                     s
> (inter)national level
     actors: political decision-makers
     information on national environmental issues
     (e.g. annual CO2-emissions per capita, acidification of soils ...)

> regional/ local level
     actors: political decision-makers, local authorities, public
     information on regional environmental issues
     (e.g. annual CO2-emissions due to industrial areas or volume of
        motor-vehicle traffic, damage to forests in the region ...)
 > organisational level
      actors: management
      information on organisational environmental issues
      ( e.g. annual CO2-emissions of one process/ facility, NO3-
        concentration  in nearby river ...)

-------
in viron mental Indicators for Organisations

                    - Avail -

Environmental Performance Indicators can be
  used to:
• identify weak points in production processes

• compare facilities, parts of organisations or
  organisations with each other (= benchmarking) or
  over timelines

• support ongoing improvement processes in areas,
  where emissions and material intensities can be
  influenced by employees

• present and analyse trends for internal purposes

• present environmental performance of organisation in
  external communication

-------
nvironmental  Indicators for Organisation
            - Selection Criteria  -

 ... for Indicators:

 •  Significance
      => concerning organisation's activities and their
       environmental impacts
 •  Sensitivity
      => to reflect changes in environmental impacts
 •  Measurability
      =» of the respective issue

-------
Environmental Indicators for  Organisation
             - Selection Criteria -

  ... for Indicator Systems:

  •  Comparability
        ^timelines comparison and benchmarking
  •  Balance
        =»good and bad aspects of performance
  •  Continuity
        ^assessment over same time units
  •  Timeliness
        ^update frequency allowing action to be taken
  •  Clarity
        ^>clear and understandable indicators

-------
environmental Indicators for Organisation
                                  —X
               - C^snoriss -
                 ^—* -—*J -^ ^—J •—* I -^^^ J J ^—J —X
         Organisation's
           activities
               Organisation's
                surroundings
  Operational
  Performance
   Indicators
Management
Performance
 Indicators
Environmental
  Condition
  Indicators

-------
Environmental Indicators for Organisation
            - Framework -
OPERATIONAL PERFORMANCE
INDICATORS
i
INPUT
I.NDJCATQRS
1,1.
Materials
1.1.1

&e
PHYSICAL
FACILITIES
AND
EqUiPMENT
INDICATORS
M

1.2.1

Installation
OUTPUT
INDICATORS
1-1
Products.
provided by
""the 	
organisation
1.3.1

S.enrices.
provided by
MANAGEMENT
PERFORMANCE
INDICATORS
(WE5)
2
SYSTEM
INDICATORS
2.-.1
tion of policies
and.
programmes
2.1.1

Conformance
FUNCTIONAL
AREA
INDICATORS
2,2
Administration
and planning
2.2.1

Pu.rchasjnjg.
and
ENVIRONMENTAL
CONDITION
INDICATORS
3
ENVIRON-
MENTAL
MEDIA
INDiCATQRS
M
3.1.1

BIO- AND
ANTHROPO-
SPHERE
INDICAtORS
M,
Flora
3.2.1

Water II f- na

-------
nv iron mental Indicators for Organisation
       - Implementation and  Use -
  Determination of significant
      environmental issues
  Data Collection and Analysis
  Development and Establishment
       of Indicator System
  Regular Update
   Regular Revision of
     Indicator System
      external
   communication
  internal controlling:
material-/ energy flows
improvement potentials

-------
Environmental Indicators for Organisations

                - Development -


... In practical context of ...

      Environmental        Environmental Reporting
    management systems    (may be part of EMS/ eg jn the
         ( E M s )              case of EMS certified after EM AS
   (e.g. EM AS 761 / 2001, ISO         761/ 2001 or ISO 14001)
           14001)

... In research projects & standardisation initiatives:


     Indicator Systems        Sector Specific Indicator
        (intersectoral)           Systems
   (e.g. ISO 14031/ TR 14032,         (EPI Finance, CEFIC
         GRI, WBCSD)            ^Responsible Care")

-------
Environmental Indicators for Organisations
  - International Standards and Projects -
General indicator systems:
-  ISO 14031 Environmental Performance Evaluation"/
   TR 14032 ,,Examples of EPE"
-  WBCSD ,,Measuring Eco-Efficiency - A Guide to reporting
   Eco-Efficiency" (2000)
-  GRI ,,Sustainability Reporting Guidelines" (2002)
Sector specific indicator systems:
-  EPI Finance (2000)
-  CEFIC Responsible Care" (started 1985)

-------
Environmental Indicators for Organisations
              - Present Use -

 > Common practice: use of a few indicators
  for external communication
  (e.g. in environmental reporting)
 > Few organisations employ full, consistent
  indicator framework as an internal
  controlling instrument
  (e.g. in environmental cost accounting)
 > Up to now, no comprehensive up-to-date
  survey on the use of indicators  by
  organisations exists

-------
               Suggestion

Compilation of an Information pool
concerning the application of environmental
indicators in organisations:
 - Which and how many indicators are used?
 - How many organisations make use of full
  indicator frameworks?
 - What are dominant motivations for use of
  indicators?

as a helpful tool for:
 - Organisations in the process of implementing
  indicators,
 - Benchmarking among organisations already
  using indicators

-------
Example
I. Operational Performance Indicators
1 . 3. Output Indie ators

1.3.3 Waste s Indie ators



Example: Pharmaceuticals &, Biotechnology
Ayentis SA, France
AKvVVVVT^-VrVv*
Hazardous Waste
in absolute
and relative
f
ngur es

Hazardous Waste Generated


{'r^nijtsfw MiiMfw
s(X)2 (Melrif law) !'}•!•&><. Vaui}^
recycled 20,346 1.001
incinerated G3.5GS 1.1 48
landfilled &GB 105

taken from: 2002 Sustainability Report

-------
             Life Cycle (Impact) Assessment

               Dr. David Pennington
                     Soil & Waste Unit
            Institute for Environment & Sustainability
                    Joint Research Centre
                    European Commission
                   (david.pennington@j rc.it)
                      '
                       •
                      '
Available Impact and Resource Consumption Indicators

-------
          Illustration of Life Cycle Assessment
Part / Process
    Design
      Mfg.
     Inputs

    Raw
    Materials
    Energy
    Water
    Packaging
                            Recycling, Energy Recovery
 Manufacture
and Assembly
System /
 Vehicle
  Use

End of
 Life

Hazardous &
Industrial
Waste



Water
Waste




Air
Emissions




Noise,
radiation, etc.

Life cycle of an automobile (Adams and Schmidt 1998)

-------
            Emissions Inventory
O)
E
CO
tO
E
HI
sAc
                                       o
                                             Gasoline
                                             Diesel
                                              Natural gaz
Jolliet et al., EPFL, Lausanne (olivier.jolliet@epfl.ch)

-------
Risk & Impacts (for Diesel Vehicles)
                             Non-cancer

-------
Comparisons: Different types of fuel use
^ 1.E-05
^£ 1.E-06
(/) 1 F 07
o 1E-°7
!_ 1.E-08
^ 1.E-09
0)
O) 1.E-10
£ 1.E-11
Q 1.E-12



























CD
O
c
CO
0



Petrol
























II
8
c
CO
o
1
c
o
z

i — i




CD
O
c
CO
O





























I I
















i i i i










8 CD CD
O O
C C C
CO CO CO
V o V
c c
o o
z z
Diesel Natural gas

         Diesel causes:  4 times more damage than petrol
                   10 times more than natural gas

-------
  Emissions to Accidents (Annual impacts)
       1.E+07
       1.E+00
            EUROPEAN UNION
                 SWITZERLAND
   — >- 1.E+04
              Emissions
  Fatal
accidents
Emissions
  Fatal
accidents
Damage of emissions on human health equivalent to 6 - 8 % fatal road accidents

-------
      In terms of Money?
For 100 km
Gasoline:
Diesel:
Natural Gas
Human health
0.7 Euro
2.9 Euro
0.3 Euro
Fuel
8.1 Euro
4.5 Euro
Switzerland per year:  380 millions Euro
(3.5 million cars, 13,790 km/car, 100,000 Euro per DALY)

-------
  Why the big
 LCA  picture?
  Natural Gas
  Extraction
  (Gas Wells)
  Natural Gas
  Extraction
  (Oil Wells)
On-Site Processing
Stage
                                        Hydrogen
                                        Production
                                        Acetylene
                                        Production
                                        Methanol
                                        Production
                   Propylene Oxide
                   (upstream not considered)
                                                       Arco
                                                      Process
                                                       Reppe
                                                       Process
                 t k > k
                        10%
                           1,4-Butanediol
                        90%
               Formaldehyde
                Production
         1,4 butanediol (EDO) derived from natural gas

(energy consumption and associated processes not shown) (U.S. EPA 1997)

-------
   Sulfur
      Sulfur
    Production
       Feedstocks
    Phosphate
      Rock
    Production
Phosphate
   Rock
:T
            Limestone
                Limestone
              Production and
              Transportation
              Fertilizer Prod.
              Packaging, and
               Distribution
              Pesticide Prod.
              Packaging and
               Distribution
Feedstocks
I
                         Corn
                       Production
                                           Brine
                        Natural
                         Gas
                                  Corn
                                 Transport
                                     Sodium
                                    Hydroxide
                                    Production
                            Hydrogen
                            Production
                           Wet Corn
                           Milling
                                                                          Glucose
                                                                       Steep Liquor
                                                             Sodium
                                                                   Hydroxide
                                               Hydrogen
                                                                   CO2
                                                                                    HCL
                                                                                    Tryptophan
                                                                                    Cysteine-HCL
                          Alternative
                        EDO Production
On-Site Processing Stage
1,4-Butanediol
                  Bio-derived EDO from  corn production
 (energy consumption and associated processes not shown) (U.S. EPA 1997)

-------
o
Q
CD
a)
o
I
1
a
4E-04

3E-04

2E-04

1E-04

OE+00

-1E-04

-2E-04

-3E-04

-4E-04

-5E-04
                                               Bio-derived Process Best
6
7
                                               Gas-based Process Best
                       WMPT PBT Non-Cancer Human Health Impact Categories
                    Process Stage    • Life Cycle
             Differences between EDO alternatives
8
       (organic emissions, non-cancer human health PBT scores)

-------
            E-02i
      I
      >
      3
>   OE+0(
      I 111
      (D
      C
      (D
      0
      o
      C
      (D
    -1E-
          -3E-02-
                       Bio-derived Process Best
                                                                          8
                                                       Gas-based Process Best
                     WMPT Non-Cancer Human Health Impact Categories
                            Process Stage • Life Cycle
                      Differences between BDO alternatives

(PBT scores vs. toluene equivalency potentials, organic emissions, non-cancer human health effects)

-------
Many Impact (incl. Resource Consumption) Categories & Indicators
Metrics
N/A
Natural Gas-Based
Processing
0
Life Cycle
6.31E-07
Bio-Based
Processing
0
Life Cycle
1.30E-04
   Land Use for Resource Extraction/Production in Acre-Years per Pound of BDO
Component
FGD Solids
Fly Ash
Slag
Depleted Uranium
Other Solids
Total
Comparison
Metric
1.67
1.67
1.04
0.17
2.22
N/A
Natural Gas-Based
Processing
2E-06
4E-06
4E-07
3E-08
0
5E-06
Life Cycle
3E-06
7E-06
6E-07
6E-08
0
8E-06
Bio-Based
Processing
3E-05
6E-05
5E-06
5E-07
4E-04
7E-05
Life Cycle
3E-05
7E-05
5E-06
5E-07
4E-04
4E-04
                  Land Used for Solid Waste Disposal in Cubic Yards.

-------
           Phases and applications of an LCA

                      (ISO14040 Series)
Focus -
             Life Cycle Assessment Framework
               Goal
             and Scope
             Definition
             Inventory
             Analysis
  Impact
Assessment
                            Interpretation
                                     Direct Applications:

                                    Product Development
                                    and Improvement

                                    Strategic Planning

                                    Public Policy Making

                                    Marketing

                                    Other

-------
Elements  of LCIA (ISO  14042)
               Mandatory Elements
  Selection of Impact Categories, Category Indicators,
              Characterization Models
             Assignment of LCI Results
        Calculation of Category Indicator Results
       Category Indicator Results (LCIA Profile)
                Optional Elements
    Calculation of the Magnitude of Category Indicator
           Relative to Reference Information
                    Grouping
                    Weighting
               Data Quality Analysis

-------
Table 1  ISO requirements/recommendations for selecting impact categories & indicators (ISO,
1999)	
ISO 14042 requirements
a) The selection of impact categories, category indicators and characterisation models shall be
   consistent with the goal and scope of the LCA study
b) The sources for impact categories, category indicators and characterisation models shall be
   referenced
c) The selection of impact categories, category indicators and characterisation models shall be
   justified
d) Accurate and descriptive names shall be provided for the impact categories and category
   indicators
e) The selection of impact categories shall reflect a comprehensive set of environmental
   issues related to the product system being studied, taking the goal and scope into
   consideration
f)  The environmental mechanism and characterisation model which relate the LCI results
   and category indicator and provide a basis for characterisation factors shall be described
g) The appropriateness of the characterisation model used for deriving the category indicators in
   the context of the goal and scope of the study shall be  described

ISO 14042 recommendations
a) The impact categories, category indicators, and characterisation models should be
   internationally accepted, i.e. based on an international agreement or approved by a
   competent international body
b) The impact categories should represent the  aggregated emissions or resource use of the
   product system on the category endpoint(s) through the category indicators
c) Value choices and assumptions made during the selection of impact categories,  category
   indicators and characterisation  models should be minimised
d) The impact categories, category indicators and characterisation models should avoid double
   counting unless required by the goal and scope definition
e) The characterisation model for  each category indicator should be scientifically and technically
   valid, and based upon a distinct identifiable environmental mechanism and/or
   reproducible empirical observation
f)  The category indicators should  be environmentally relevant
g) It should be identified to what extent the characterisation model  and the characterisation
   factors are scientifically and technically valid

-------
Table 2 General items to address when discussing category indicators	
1)  Essentials (extent of quantification, regionalisation and comprehensiveness, incl.
    environmental relevance) of the indicator set
2)  Sensitivity of the indicator for the intervention changes
3)  Description of environmental mechanism and characterisation model, incl. extent of relying
    on reproducible empirical observations and scientific/technical validity
4)  Extent of representation of the category endpoints through aggregated interventions
5)  Extent of and description of value choices and assumptions (on the levels of model and
    data)
6)  Extent of double counting and other consistency issues
7)  Applicability regarding the data available

-------
              Models & Environmental Mechanisms


Life cycle inventory results
   LCI results assigned
   to impact categories
Impact
category^
               Characterisation model
    Category indicator
                 Environmental relevance
Example

SO2, HC1, etc
(kg/functional unit)

Acidification

Acidifying emissions
(NOx, SOx etc.
assigned to acidification)

Proton release
(H+ aq)
                                    03
                                    B
                                    a
                                    o
   Category endpoint(s)
              -forest
              -vegetation
              -etc.
                       1

-------
Simple (linear) calculations

Category
Indicator =

Values

( CO2 CC14 CBrHl} ,
( CO2
GW 1 1400
• CC/4
OD 1.1 0.6

^HT 14000 12000 J ^
X /"
2100%^ (GW 2800 kgc02_equ
0 5 y^p- = OD 0 73 y^p-
* <*^ 5s*^ -* — ' " • * *-^ * v/-** (~* TT(~^ 11 ,0 /7i
-^/'...ii-e^
0 3/ce . //7 I0600£e
V7 • «_/ / ViL / \ -L -L -L ±\J\J\J\J / ViL /^ 7, //?7/i/? /?
o ^/ \ c? toiucnc — ci
Characterisation factors LCI results Category indicators
Weighting:

f f^ TTT~ ^ o r\ r\ / -
, , I GW 2800 kz^« ._. 1
Weighted
Results I
GW OD HT] — — /,
• OD 0.73£gr/7ril v,
0.2 800 0.4 ZCFCll-equ
V """ y ^ 10600 feto/__^J


= 560 + 584 + 4240 = 5384


Category weights Category indicator values Weighted indicator results

-------
Interventions
                 Physical
                 impact
                 categories
                 Impact
                 midpoints
abiotic extractions -~-~_~_
                       	         ^
1"Yir\fir» p*vir'cirvHrvnc                                          *      ""^
biotic extraction^
land use
(transform.
& occupationj\
                         loss of habitat
       \ \
     'x\ow<
Endpoint
categories

abiotic resource
depletion    \N
               \
resource (&land)
competition

global loss of
biodiversity
    r
non-global
Areas of
protection
ground- \tat<
water  ^  \
extraction   \
        surface si
        and other
        changing la^id
        characteristic*
                 local (rare)
                 species diversity
         itats \     T             ^^j? loss of
              > \   *     ^-^^^^    biodiversi
                 ecosystem
less (free)        diversity
biomass
production
                                                                                       natural
                                                                                       resources
                         erosion
                         soil compaction
                 soil degradation
                         on landscapes
                                                                                       biodiversity^
                                                                                       & nat landscapes
     human welfare
                         morphological impacts ^ aesthetic impacts on landscapes
                                                  geological impacts
                                                  impacts on cultural history
emissions
                         other impacts —* other endpoint
                                          damage to
                                          humans
                                                               man-made
                                                              ivironment
 human health

-------
                Midpoint or endpoint indicators?
    Emissions (CFCs, Halons)
Chemical reaction releases Cl- and Br- which destroys ozone
                      Based on chemical's reactivity / lifetime
                MIDPOINT measures ozone depletion potential (ODP)
                     Less ozone allows increased UVB radiation
                       which leads to following ENDPOINTS
 skin cancer
            crop damage
                                                                   cataracts
marine life damage
           immune system suppression     j  |     damage to materials like plastics
                     (Ozone Depletion Example)

-------
stressor


insult


stress


consequence


value lost

Benzene emissions


t C6H6 concentration


C6H6 exposure


leukemia


YLL, morbidity, suffering
 Impact chain
   ace. To
Holdren(1980)
Human health
 impact chain
                                           HTP
                                                       DALY
Guinee & Heijungs
     1993
Hofstetter
 (1998)
           (Toxicological Effects on Humans Example)

-------
         Temporal/Spatial Specific Indicators?
      0,001
DO

c
o
"J
o

T3
O
     0,0001
    0,00001
o  0,000001
  0,00000

               8  11  9  12 19 13 14 5 10 17 18 16  6  15 4  2  3

                            Emission Zone
      (Human intake example for different zones in Japan)

-------
 Many Tools Exist; Models, Databases,...
(Problems: heterogeneity, quality, state-of-the-art, ....)
/' P2P 1 mpacts HH E3 1
CAS No. 50-00-0
Preferred Name Formaldeh
! Edit Data i Print Chemical
yde
Acid Rain Precursor N Fine Fiber N
Aquatic Toxicant
Global Warmer N
BOD V Hazardous Waste Y
Carcinogen
Human Health Toxicant
COD Y Metal N
Corrosive N Nutrient N
Dissolved Solid N Odorant Y
Human Health Non-Car<
Human Health Carcinog
Aquatic Toxicity
Bio Accumulation
Persistence
;inogen 1 ^,/LJDT r t «
WMPT Cutoffs
en 2
^ Persist Bio^
, 3 3
1 2 2
1 1


Ozone Depleter N
Particulate N
Pathogen N
Radioactive N
Smog Former Y
Solid Waste N
Suspended Solid N
Change a WMPT Cut-off
ice Toxicity Metal
3 3
2 2
1 1

Clicking on a blue name will bring up a definition; Black values are defaults.
Red values are user-supplied. Restore returns them to VMPT values, if available, or to default values.
values are calculated using VMPT data.
These cannot be changed directly. Changing VMPT data or cut-offs can change them.

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        JOINT                      Conclusions
        RESEARCH
        CENTRE
EUROPEAN COMMISSION
(Recommended LC(I)A literature)
 Metrics for environmental comparison of process alternatives in a holistic framework.

Pennington D.W., Norris G., Hoagland T. and Bare J., Process Design Tools for the
Environment, Sikdar S.K. and El-Halwagi M.M., editors, Taylor and Francis (UK),
2001

Life-cycle impact assessment: Striving towards best practice.

Udo de Haes H., Jolliet O.,  Finnveden G., Goedkoop M., Hauschild M., Hertwich E.,
Hofstetter P., Klopffer W., Krewitt W., Lindeijer E., Mueller-Wenk R., Olson S.,
Pennington D., Potting J., Steen B. SETAC Press, Pensacola, Florida, US. 2002.

Life Cycle Assessment: Current Impact Assessment Practice (Part 2)

D. W. Penningtonl*, J. Potting2,  G. FinnvedenS, E. Lindeijer4, O. Jollietl, G.
Rebitzerl., Environment International, Submitted.

ISO 14040 Series (especially 14042)

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NT \ IT
'JVondhcim
         Sustainability Indicators and
      Reporting Mechanisms in Regions
                    Annik Magerholm Fet
         Norwegian University of Science and Technology (NTNU)

         NATO CCMS Pilot Study on Clean Products and Processes
                     2003 Annual Meeting
                       Cetraro, Italy
                       May 11, 2003

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IS T \ IT
'JVondhcim
Background:
         The European Government recognizes the importance
         of coordinated sustainable management actions,
         however, efficient tools to harmonize measurements in
         different regions are still lacking.
         A proposed project "Sustainability Reporting in
         European Regions" (SUREER) will fill this gap by
         establishing Sustainability Reporting (SR) in European
         regions, based on the "triple bottom line" indicators of
         the Global Reporting Initiative (GRI).

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IS T \ IT
'JVondhcim
                       Outline:
        Introduction to the proposed project SUREER
        Discussion on how this can contribute to the
        development of a set of sustainability
        indicators
        Recommendations for Future Activities for the
        NATO CCMS program

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IS T \ IT
'JVondhcim
            The consortium consists of:
            Norwegian University of Science and Technology, Norway,
            represented by Prof. Annik Magerholm Fet (Coordinator).
            Kaunas University of Technology, Lithuania, represented by
            Prof. Jurgis K. Staniskis.
            Technical University Graz, Austria, represented by Prof. DI Dr.
            Michael Nardoslawsky.
            University of Kaiserslautern, Germany, represented by Prof. Dr.
            Heiner Miiller-Merbach.
            Aristotle University of Thessaloniki, Greece, represented by Dr.
            George Gallios.
            University of Malta, Malta, represented by Prof. Lino Briguglio

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IS T \ IT
'JVondhcim
    Objectives of the project

The main objective of SUREER is to establish
a framework for Sustainability Reporting (SR)
in small European regions, consisting of an
indicator database (IDA) integrated in a
reporting procedure (Generic Process Model,
GPM) delivered as manual for SR users, which
is applicable for the organizations in all
regions.

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IS T \ IT
'JVondhcim
      Achievable  main  goals

 The development of an indicator database (IDA) including
-    core indicators,
-    additional indicators for regions and
-    business specific indicators
-    Further a set of cross cutting indicators and systemic indicators.
 The development of an evaluation method for the application of
 indicators.
 The development of a generic process model (GPM) for a common
 procedure guideline for sustainability reporting in different
 geographical regions.
 The development of an evaluation method for the implementation of
 Sustainability Reports
 Combined sustainability reports for at least 6 European regions.
 Sustainability reports for at least 36 SMEs (6 in each partner country)
 Capacity building among universities, communities and companies,
 transferred through the cooperative work among participants from
 different regions in Europe.

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IS T \ IT
'JVondhcim
Further goals
         Indicate core indicators that can be used in different
         sized organizations.
         Develop sector specific indicators for particular
         industries.
         Develop cross-cutting indicators that present
         environmental performance together with one of the
         other two dimensions in the triple bottom line.
         Develop systemic indicators that link the companies
         and communities activities.
         Reach quality improvement over time by outlining the
         options to move from moderate to good and high
         application levels of indicators.

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NT \ U
'JVondhcim
                                                   Sustainability
                                                   reoortina
                                                Socio-economic indicators

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IS T \ IT
'JVondhcim
Global Reporting Initiative (GRI)

- guidelines

   •  the first global framework for comprehensive
     sustainability reporting, encompassing the "triple
     bottom line" of economic, environmental, and social
     issues.
   •  will become the generally accepted, broadly adopted
     framework for preparing, communicating and
     requesting information about corporate performance.
   •  give guidance to reporters on selecting generally
     applicable and organisation specific indicators, as well
     as integrated sustainability indicators. Forward-looking
     indicators and targets for future years are also included.

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IS T \ IT
'JVondhcim
             THE INDICATOR

               FRAMEWORK

Category: The groupings of economic, environmental, or social issues
   of concern to stakeholders
Aspect: The general subsets of indicators that are related to a specific
   category. A given category may have several aspects, which may
   be defined in terms of issues, impacts, or affected stakeholder
   groups.
Indicator: The specific measurements of an individual aspect that can
   be used to track and demonstrate performance. These are often,
   but not always, quantitative.
According to GRI, aspects and indicators are derived from an
   extensive, multi-stakeholder consultative process.

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                                         CATEGORY
                                                     ASPECT
NT \ U
ThMidhcim
Catego-
ries  and
aspects:
                                         Direct Economic Impacts
                           Customers
                           Suppliers
                           Employees
                           Providers of capital
                           Public sector

                           Materials
                           Energy
                           Water
                           Biodwersity
                           Emissions, effluents, and waste
                           Suppliers
                           Products and services
                           Compliance
                           Transport
	Overall

 Labour Practices and DecentWork  Employment
                           Labour/management relations
                           Health and safety
                           Training and education
                           Diversity and opportunity
                                                                   Strategy and management
                                                                   Non-discrimination
                                                                   Freedom of association and collectrve bargaining
                                                                   Child labour
                                                                   Forced and  compulsory labour
                                                                   Disciplinary  practices
                                                                   Security practices
                                                                   Indigenous rights
                                                                   Community
                                                                   Bribery and  corruption
                                                                   Political contributions
                                                                   Competition and pricing
                                                                   Customer health and safety
                                                                   Products and services
                                                                   Advertising
                                                                   Respect for  privacy

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IS T \ IT
'JVondhcim
       PERFORMANCE INDICATORS
      The GRI performance indicators are classified along the
        following lines:
      Core indicators (or general applicable indicators) are
        those relevant to most reporters; and of interest to most
        stakeholders.
      Additional indicators (or business specific indicators) are
        viewed as leading practice in economic, environmental,
        or social measurement, and providing information of
        interest to stakeholders who are particularly important
        to the reporting entity.

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IS T \ IT
'JVondhcim
INTEGRATED PERFORMANCE

             INDICATORS

A fourth dimension, grouped in
Systemic indicators related to the activity of an
  organisation to the larger economic, environmental,
  and social systems of which it is a part. For example,
  an organisation could describe its performance relative
  to an overall system.
Cross-cutting indicators directly related to two or more
  dimensions of economic, environmental, and social
  performance as a ratio. Eco-efficiency measures are the
  best-known examples

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\T
ThiiH
WBCSD Eco-efficiency Indicators:
       The Framework
1. An overview of environ-
  mental and value-related
  categories aspects and
  indicators
                                    Business Specific
                                    Indicators Selection

                                   Generally Applicable
                                   HH Indicators
                                             Profile
                                         Gen. applicable
                                           Indicators
                                                                 Indicators
                                                                selected by
                                                                the company
                                  2. The selection of indicators
                                    that are relevant and
                                    meaningful to a specific
                                    company
                                     3. Report generally
                                       applicable and
                                       business specific
                                       indicators
      WBCSD

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N T \ U
The Eco-efficiency Concept
'JVondhcim
    Eco-efficiency  = product or service value
                   environmental influence
    Eco-efficiency indicator = economic performance indicator
                        environmental performance indicator

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N T \ U
'JVondhcim
Methodology
        A systems engineering methodology (SEM) moving from the
        •   analysis of the regional systems and
        •   the identification of stakeholders' priorities to
        •   the definition of the requirements for indicators,
        •   further to the development and selection of indicators, which are
           exploitable to improve the systems and
        •   to the development of the indicator database and
        •   the reporting procedure.

        The indicator database will reflect the mutual process between
           legislation and organizations' activities. This will be accomplished
           by analysing and developing indicators from the bottom to the top
           and vice  versa

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NT \ IT
'JVondhcim
                    s  &
                   -9  o
                   •o 2
                                              Step 1.
                                   Identify Needs for  Indicators
                                             Step 2.
                                  Define Indicator Requirements
                                             Step 3.
                                        Specify Indicators
                                             Step 4.
                                  Analyse and Optimise Indicators
                                             Step 5.
                                  Design an indicator system and
                                        complete reporting
                                             Step 6.
                                Verify the indicator application anc
                                       test the indicator use
   Requirements to
      Reporting
 Iterative process I
 > Trade off for strategies
 > Negotiate within the
 frame of different needs
 > Discuss solutions with
 respect to ethics,  politics
 and technology
Iterative process II
> Prove via modelling
> Application
> Questionnaires
> Training/instruction/
formation
                                Exploitation: Use the indicators for new
                                product design and
                                innovative decision- and
                                policy making

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IS T \ IT
'JVondhcim
"Bottom up" versus "top down"
      From company reporting
        and indicators to
      Sector reporting and
        indicators to
      Municipal reporting and
        indicators to
      Regional reporting and
        indicators

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IS T \ IT
'JVondhcim
          Reporting  structure
                                         GPM as a
                                         Roadmap
 Companies
Indicators and
  Reporting
                                                             Sustain-
                                                              able
                                                            European
                                                             Regions
Negotiating
 priorities,
aspects and
  develop
 indicators
                                  Sustainability
                                    Reporting
           Municipalities
           Indicators and
             Reporting
                               Indicator
                               Database

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IS T \ IT
'JVondhcim
 Suggestions for NATO-supported
                  project:

1.   Agree about definitions and terminologies for
    performance indicators
2.   Test a set of core-indicators in different regions
3.   Develop/test business specific indicators
4.   Develop systemic indicators for municipalities and
    regions
5.   Test a reporting structure for a few regions
6.   Use/develop criteria for sustainability regions and
    evaluate the reports against these

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Environmental Management

Accounting
Gyula Zilahy

llth May, 2003




         Http://hcpc.bke.hu  e-mail: cleaner@enviro.bke.hu
                                       CO
                                       o
                                       o
                                       (N
                                       Q
                                       en
                                       u
                                       u
                                       o
                                       H

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Financial considerations and the

environment

                                                   o
                                                   o
                                                   (N
Impacts of the environment on the economy:


 -  Limited resources: raw materials and energy


Impacts of the economy on the environment:               3


 -  Excessive use of resources                            3
                                                 en

 -  Pollution of the environment                            -I
                                                 k
                                                   o
                                                   u
                                                   o

                                                   I
           Http://hcpc.bke.hu  e-mail: cleaner@enviro.bke.hu

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The need for quantification
                                                           CO
                                                           o
                                                           o
                                                           (N
There is a need to quantify the changes in the environment

in financial terms, i.e. in money units:                        |

 -  To gain a more reliable picture of human welfare;                 u

 -  To be able to compare different solutions;                       1
                                                          m
 -  To  help decision-makers  involve environmental  issues  in their    ;§

    decisions.                                               ™
                                                           o
                                                           u
                                                           o

                                                           I
             Http://hcpc.bke.hu   e-mail: cleaner@enviro.bke.hu

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The definition of EMA

                                                  o
                                                  o
                                                  (N
                                                  I
                                                  en
                                                  +->
                                                  o
"a sub-area of accounting that deals with activities,

methods and systems for recording, analyzing and
                                                 >MF

reporting the environmental issues  and impacts    >

and  ecological  impacts  of  a defined economic

system." (Schaltegger)                             %

                                                 u
                                                 o
                                                 o

                                                 I
         Http://hcpc.bke.hu   e-mail: cleaner@enviro.bke.hu

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                  Levels of EMA
   Orszagos szinten
Vallalati szinten

Source: Csutora, Vallalti kornyezetvedelmi koltsegek szambavetele, III.

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   The two main directions of EMA
Cost allocation
Investment

appraisal
         Http://hcpc.bke.hu  e-mail: cleaner@enviro.bke.hu
                                            CO
                                            o
                                            o
                                            (N
                                            Q
                                            en
                                            u
                                            u
                                            o
                                            H

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Why companies should use EMA?

many environmental costs can be significantly reduced or
                                                     o
                                                     o
  eliminated
x environmental costs may be hidden in overhead costs         |
x more accurate costing and pricing is possible                ^
x improved environmental performance                      J
x competitive advantage                                 I
x can support an overall environmental management system      ss
                                                     o
                                                     u
                                                     o
                                                     I
            Http://hcpc.bke.hu   e-mail: cleaner@enviro.bke.hu

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Why EMA has not been used before?

environmental costs used to be low;

saving opportunities used to be low;
     "
accounting itself costs money;

accounting is a conservative discipline
                                            o
                                            o
                                            (N
                                            a
                                            t.
                                            O
                                            u
                                            o

                                            I
          Http://hcpc.bke.hu  e-mail: cleaner@enviro.bke.hu

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Different types of environmental costs
  Conventional costs

  Hidden costs

  Contingent costs

  Intangible costs
  External costs


g
^^^^^
^•M •
o
                                         o
                                         0)
           Http://hcpc.bke.hu   e-mail: cleaner@enviro.bke.hu
CO
O
o
(N
        Q
                                                  en
        u
        u
        o
        H

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Caracteristics of different types of
environmental  costs
                        Conventional Hidden Contingent Intangible Social
Present costs
Future costs
The company pays for the costs
The society or the environment
bears the costs
We know the exact amount
We can estimate the cost
They are buried in the overhead

             Http://hcpc.bke.hu   e-mail: cleaner@enviro.bke.hu
o
o
(N
Q
o
—<
1—I
IH
cn
U
O
H

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  Examples for  the different  cost types
 Conventional
Equipment costs
(buildings,
equipment, site
preparation);
Raw materials;
Direct labour
cost;
Utilities;
General sales and
administrative
costs.
     Hidden
Cost of
documentation
control of
environmental
management
systems,
Compensation of
workers;
Environmental
insurance costs;
Fines;
                   Contingent
                 Future
                 compliance
                 costs,
                 Penalties/fines,
                 Response to
                 future releases,
                 Remediation,
                 Property
                 damage,
                 Personal injury
   Intangible
Corporate image,
Relationship
with: customers,
investors,
insurers,
professional
stuff, workers,
suppliers, and
regulators.
                 damage,
Lost workdays due  Legal expenses,
to sickness and     Natural resource
injuries,           damages
Waste disposal
costs.
   Http://hcpc.bke.hu    e-mail: cleaner@enviro.bke.hu
    Social
External or
social costs,
Medical costs
of cancer
patients,
Damages
caused in
natural
resources.
CO
o
o
(N
Q
                             en
                                                                           u
                                                                           u
                                                                           o
                                                                           H

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nvestment appraisal
                                                 CO
                                                 o
                                                 o
                                                 (N
Profitability indicators:


   x Payback period                             |
                                               u
   x Net present value (NPV)                      g


   x Internal Rate of Return (IRR)                  f
                                               ,—i
                                               •i—i
                                               OH

                                               1
                                               8
                                               O

                                               I
        Http://hcpc.bke.hu  e-mail: cleaner@enviro.bke.hu

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Cost Allocation




           Http://hcpc.bke.hu   e-mail: cleaner@enviro.bke.hu
                                                   CO
                                                   o
                                                   o
                                                   (N
                                                   Q
                                                   en
                                                   u
                                                   u
                                                   o
                                                   H

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 Traditional allocation  of overhead  costs
                     Administration
       50,000 EURO
100,000 EURO      100,000 EURO
_J	L_
       Toxic waste
       product "B"
       50,000 EURO

       _J
                          Overhead costs
                          300,000 EURO
           50,000 hour

50,000 hour
>
f
Product A
Direct labor hours
>
f
Product B
           150,000 EURO
 150,000 EURO
Source: Csutora, Vallalti kbrnyezetvedelmi kbltsegek szambavetele, III.

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Consequences of traditional method

Polluting products seem more profitable;

  Clean products seem less profitable;
  False signals to decision makers;

  Polluting products are favoured.
                                              o
                                              o
                                              (N
                                              o
                                              ^
                                           I

                                            o
                                            u
                                            o

                                            I
        Http://hcpc.bke.hu  e-mail: cleaner@enviro.bke.hu

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   Suggested allocation of  costs
       50,000 EURO

            L_
                       Administration
100,000 EURO
                               dc waste
                               .duct "B"
            50,000 hour
             Product A
100,000 EURO

_J
50,000 EURO
                           Overhead costs
                           250,000 EURO
                    50,000 hour
                          Direct labor hours
                         Product B
           125,000 EURO
Source: Csutora, Vallalti kbrnyezetvedelmi koltsegek szambavetele, III.
                       125,000 EURO
                       + 50,000 EURO
                       175,000 EURO

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  Cost Allocation: Step 1
         Cost
         Center 1
Cost
Center 2
Cost
Center 3
                                    50kg
                                    waste
                                                 Product A
                                   Waste disposal
                                   cost: 800 EURO
Source: Csutora, Vallalti kbrnyezetvedelmi kbltsegek szambavetele, III.

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Cost Allocation: Step 1
   Cost Center 1.





   Cost Center 2.
   Cost Center 3.
                 Waste
 100kg
 50kg
 50kg
           Cost of inceneration
400 EURO
200 EURO
 200 EURO
      Total:
200kg
 800 EURO

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 Cost Allocation: Step 2
Source: Csutora, Vallalti kbrnyezetvedelmi kbltsegek szambavetele, III.

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Cost Allocation: Step 2
            Product A    Products
Total
Cost Center 1 .
Cost Center 2.
Cost Center 3.
Total:
50% 50%
200
200
40% 60%
80
120
70% 30%
140
60

420EURO
380EURO
400 EURO (100 kg)
200 EURO (50 kg)
200 EURO (50 kg)


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Results of Better Cost Allocation

  departments will get a clear picture about their
  environmental costs,                               B
  if these costs are significant, the department manager  H
  will feel encouraged to reduce these costs, which      1
                                                   •4-"
  may lead to more efficient operation and less          |
  environmental pollution.                            s
               f                                    u
                                                   u
                                                   o
                                                   I
           Http://hcpc.bke.hu   e-mail: cleaner@enviro.bke.hu

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Environmental Management

Accounting
Gyula Zilahy

llth June, 2002




         Http://hcpc.bke.hu   e-mail: cleaner@enviro.bke.hu
                                       CO
                                       o
                                       o
                                       (N
                                       Q
                                       en
                                       u
                                       u
                                       o
                                       H

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Prposal for co-operation -1
    Needs

       training of trainers in indicators and EMA
       Implementation of EMA at the company level
                                                CO
                                                o

                                                (N
                                                 »\
                                                O

    Resources of the HCPC

                                                       ^
Training material in Hungarian and in English           I
Experience in training of trainers                     I
Some experience in implementation                   I
                                               \«/
                                               I
     Http://hcpc.bke.hu   e-mail: cleaner@enviro.bke.hu

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Prposal for co-operation - 2
                                                      CO
                                                      o
                                                      o
                                                      (N
Proposed project: 2 phases

    Phase I.: train-the-trainers                          I

       Trainers from NATO CCMS partners                  ^

    Phase II.: train company representatives             I

   *   Trainings                                        £
                                                      co
   *   Implementation of EMA                             S

       Preparation of case studies, dissemination              o

                                                      I
            Http://hcpc.bke.hu   e-mail: cleaner@enviro.bke.hu

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    TRACI - Tool for the
Reduction and Assessment
   of Chemical and other
  Environmental Impacts
    NATO CCMS Pilot Study on
   Clean Products and Processes
        Annual Meeting
         May 11,2003

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r
    TRACI - Background
     Characterize and compare the potential
     environmental effects of various
     scenarios
     Promote the use of
      • Consistent set of metrics
      • Standard and scientifically defensible impact
       assessment methodology

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r
   TRACI - Applications
     Process design comparisons
     Life cycle impact assessments (LCIAs)
     Sustainability metrics comparisons
     Design for environmental assessments
     Environmentally preferable products
     comparisons

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r
    TRACI - Metrics
  Ozone depletion
                       Global warming
  Acidification
                       Eutrophication
  Photochemical smog
                       Human health - cancer
  Human health
  noncancer
                       Human health critera
  Ecotoxicity
                       Fossil fuel use
Land use
                         Water use

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r
    TRACI - Methodologies

    • Consistent with previous EPA modeling
      assumptions
    • Modeling assumptions minimized by the use
      of midpoint modeling
      Input parameters consistent with U.S.
      locations used
      Modular design allows the use of
      sophisticated impact assessment methods

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Inventory of Stressors
Land Use
Chemical Emissions
Water Use
Fossil Fuel Use
                Impact Categories
                Ozone Depletion
                Global Warming
                Acidification
                Cancer
                Noncancer
                Criteria
                Eutrophication
                Smog Formation
                Ecotoxicity
                Fossil Fuel Use
                Land Use
                Water Use
 TRACT
Tool for the Reduction and
Assessment Of Chemical and
Other Environmental Impacts
      Characterization    ^
                  R
          Air
      * J   \
           4
               :+ I)
                \
                                Ozone Depletion
  Global Warming
Cancer
 Option A     option B
 ^ ».•
re\

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Q:  How did we minimize assumptions in modeling?
A:  Model at the midpoint level.
  Emissions (CFCs, Halons)
     Chemical reaction releases Cl- and Br-
                       CI-, Br- destroys ozone
           MIDPOINT measures ozone depletion potential (OOP)
           ^                                          ^

              X                                    N
                Less ozone allows increased UVB radiation
                  which leads to following ENDPOINTS
 skin cancer
          crop damage
                                                        cataracts
        marine life damage
        immune system suppression
damage to materials like plastics

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TRACI - Software, User's Guide,
and Background Paper
• Download software from:
  www.epa.gov/ORD/NRMRL/std/sab/iam traci.htm
  User's Guide and AlChE technical paper
  also available
  For more information contact:
     Jane Bare (bare.iane@epa.gov)

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         NATO/CCMS Pilot Project
       on Clean Products and Processes
            Cetraro / Italy, 11 to 15 May 2003
        iffn and Simulation of
     nvironmental Conscious
       Chemical Process
Teresa Mata, Raymond Smith, Douglas Young, Carlos Costa
      Laboratory of Processes, Environment and Energy Engineering

        FEUP - Faculty of Engineering of the University of Porto

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Presentation Overview
           Presentation of two cas
                              dies:
               st case
               Fugitive em
                         /ersus operating conditions
            •/ 2nd case study
               Heat integration and process economi
               in the hvdrodealkvlation (HDA) of toluene
                                           izene
LEPAE
                                                     IPEQ/FEUP

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       1st case stud
 Fugitive Emissions versus
   Operating Conditions:
Catalytic Reforming Process
LEPAE
                            IPEQ/FEUP

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Study Objectives
         to examine different
         the reforming proc
ooerating conditions for

                e the reformate
         to evaluate the PE

-------
Evaluation  of the PEI's
    U. S. EPA "Waste reduction (WAR) algorithm" (8 PEPS categories):
              iman toxicity by ingestion and inhalation
              jman toxicity b
            Aquatic toxick
            "*" Testrial toxl
            Global warming
            ^one depletior
               id rain and
               log formation
  Note: These categories are combined in order to obtain a total PEI index using weighting factors currently all set
    equal to 1
 LEPAE
IpEQ/FEUP

-------
Diagram of the Reforming Process
              compressor
                      HA
  Naftha         Hx
         reactor

tower
                                   Reform ate

-------
Reforming:  chemical reactions
   Mole
   fraction
   profiles
             0.25
                 Aromatics
             0.15
                                                        Iso-paraffin
                    Ciclohexanes
                     Nonane
             0.05
Octane
                                         Hexane    Heptane
                         Ciclopenthanes
                               Reactor distance (meters)
   Catalytic reforming consists of diverse reactions:

   • dehydrogenation of naphthenes to aromatics
   • dehydrocyclization of paraffins to naphthenes
   • isomerization of paraffins and naphthenes
  dealkylation of alkylaromatics and
  hydrocracking of paraffins and naphthenes

-------
Reforming:  design & simulation
            For the simulations of Reforming:
             ^ Reactor type: adiabatic
             * Reactor length : 15 meters
             * Reactor diameter: 0.8 meters
               Total volume : 7.5 m3
               Mass of catalyst: 6818 k~
             - Bulk density : 1000 kg/n
               iperatun
                        chemical reactions and -J3 components
                     500,1500 e 3000 kPu
.15K e 813.15K
            Flash overhead recycling: 0, 20, 50 e 80°/
   LEPAE
                    IpEQ/FEUP

-------
RON of reformate
    %% p
RON  %%
= 500kPa V
       733 0

       * • • • ^ recycled
                     p = 1500kPa%%*
                            » •/'recycled
                                           • • " % recycled

-------
Fugitive  Emissions
       P = SOOkPa   .'
  kg/year
l.E+07 '

8.E+06 "

6.E+06

4.E+06 '^
2.E+06 '

O.E+00 -
    V P = ISOOkPa
  kg/yea
l.E+071

8.E+06 "
6.E+06
4.E+06

2.E+06
O.E+00
         773.15
         T(°K)
                   % recycled
        773.15
        T(°K)
813.15
              kg/ye
             l.E+07

             8.E+06'
             6.E+061
             4.E+06
             2.E+06-
             O.E+00
                    P = 3000kPa
                                            % recycled
                                                       733.15
773.15
T(°K)
                                            % recycled

-------
Potential  Environmental Impacts
     P = SOOkPa
impact/y ar
l.E+07
6.E+06
4.E+06
2.E+06
O.E+00
    * % % ».
                          P = ISOOkPa
impact/year * *
       773.15
                20
                % recycled
                      6.E+06
                      O.E+0(
    T(°K)
          813.15
    733.15 ?73>15
    T(°K)
                                    •'"SO
                                    0 % recycled
                                813.15
                                           impact/i
                           P = 3000kPa
                           %»•»*
                      l.E+07
                      8.E-KJ6 i
                      6.E-KJ6'
                      4.E+06
                      2.E+06'
                      O.E+00'
                                               T(°K)
                                                  773.15 813>15
                                                           % recycled

-------
Potential Environmental Impacts
              compressor
   Naftha
                                 tower
        reactor
                                  Re for mate
                                    IpEQ/FEUP

-------
Conclusions
        The amount of fugitive emissions and PEIs depend:
           on the magnitude of the stream flowrates through the process,
           on the stream chemical content and
                    of streams a
                  >f process equipment (e.g. valves, flanges, compressors, etc.)
   LEPAE
[bEQ/FEUP

-------
Conclusions
         This study indicates that more recycling is not always a better solution
         for waste minimization.
         In this case study to recycle means larger stream flowrates through
         almost the entire process and more equipment,  which  increase the
         fugitive emissions and their PEIs.
         Also, if recycle is increased and more pieces of equipment need to
         added the capital and operating costs of the process will also increase.
LEPAE
                                                                 IPEQ/FEUP

-------
Conclusions
        The RON of the reformate increases with T and P, however it decreases as
        the % of the flash overhead recycling increases.
        With this  study information on research octane  numbers and fugitive
        emissions an engineer could devise an operating policy that obtains desired
        products while minimizing PEIs.
        In particular, there are tradeoffs between higher  octane numbers and
        potential environmental impacts at higher temperatures and pressures, while
        increased  recycling reduces octane number and increases  potential
    LEPAE
IpEQ/FEUP

-------
           2nd case stud
Heat Integration and Process

          Economics:
Hydrodealkylation (HDA) of Toluene to Benzene
LEPAE
                               IPEQ/FEUP

-------
Study Objectives
                           IpEQ/FEUP

-------
Diagram of the HDA Process
            .
             ......
                             compressor
     toluene
              furnace
         /"\  trtli
J^llMiM
         pump
                    reactor
                     benzene „
                   tower 3
                                 H2 / CH4
                                       valve
               tower 2
                                   tower 1
                biphenyl

-------
HDA: chemical reactions
LEPAE
                               IPEQ/FEUP

-------
The HDA Process
        toluene
                mixer
           diphenyl
furnace
reactor
                    benzene
                            4 "•
                            A.JJ
                         HX2
                    tower 3
                                  compressor
                                     HX1
                                    H2, CH4
                                  tower 2
               spliter,
                                             valve
                                             tower 1
   LEPAE
                       IpEQ/FEUP

-------
The HDA Process
                mixer
                                  compressor

                             2 s s s s s s j j
              pump  ,
                   benzene
03
furnace ^ reactor   /  HX1



            H2, CH4
                         -©<
                         HX2
           diphenyl
                    tower 3
                                 tower 2
                     spliter
                                             flash
                                             valve
                                            tower 1
   LEPAE
                             IpEQ/FEUP

-------
The HDA Process
       toluene feed
        H, feed
                             compressor
              mixer
                HX3
                     furnace
IXI
reactor
  i.xflash
HX1  y
|M^< pump
1 *J-
J*



.H
$y
diphenyl ^ 	 ^

_|- j
^
—
—
20
~22~
^S
Y
J

i J" J"
/'
^
^ —



towe
\l
<=

j^
i
^
1
.
.
1
1
•
i
s
1
1
•
:r3
l-

\
h


'
|
k

-3-@^-3-,
HX2 J— ^3
t C-l2
t
J
1
1
1
1
1
1
1
1
1
r*
•
/
^^^^^^^ ja
J-J-J-J-J-J-J..^^



n
X
^^
3
4
_5_
6
_Z_
8
9
10
_LL
_12_
3
4
_§_
7
8
9
0
1
22_
23
24
f
J




^

Itowpr ^



H2, CH4

-------
The HDA Process
               mixer
          diphenyl
HX3
                 benzene
    u
                  tower 3
             I
              compressor
                ^f.
                                        spliter •/j|
                                         I  ^N - ^
                             reactor     HX1
                           -2F
£T
                               tower 2
                                         i tower 1
                                                IpEQ/FEUP

-------
PEI's of the Process
                    Total PEI/yr
16xl













^ — 1









                     a
b        c
ALTERNATIVES
d
           The effect of heat integration on total PEI is relatively small between these alternatives.
   LEPAE
                       IpEQ/FEUP

-------
PEI's of the Process
                            b       c
                            ALTERNATIVES
               Fugitive emissions increase when more integrated the process is.
   LEPAE
IpEQ/FEUP

-------
The HDA Process
            f^sTpump  ,
t
5
6
8
9
0
6
8
9
0
^S
V
>
4



1
!
.
,
i
•
•
i
•
•L
1
•
H ^ ,
H ^J
!
H
H
H
'/ ^^1
, J.J.J.J.J.J.- .^^
^ .i jjjj -jjj
                                     ,iH

                                     ii'J
                                     !l'J
                                     .iH
                                     ,iH

                                     ,nj
                                               er
           diphenyl
              One more heat exchanger and process streams added without replacing others.
                                                    IpEQ/FEUP

-------
PEI's of the Energy Generation
              Total PEI/yr
















D Energy
D Process














              a
b      c
ALTERNATIVES
d
  LEPAE
                [pEQ/FEUP

-------
PEI's of the Energy Generation
                   Total PEI/yr
2.0xl(f

1 ^Ytfi7
A.OAAU
1 ^vlfi7
I.^XIU
_/;
O fW1 ff
o.UXlU
4f\ ~t rO
.Oxlu
O.OxlcP

















*

j


a


D Energy
D Process



>
_N,


i,i •
b c
ALTERNATIVES









J^
d











             Contribution to the PEI's due to energy generation decreases as the level of energy
                  integration increases since energy consumption decreases.
   LEPAE
[DEQ/FEUP

-------
Total PEPs of the Process and Energy Generation
         For the combined PEI of the process and of the energy generation, alternatives b, c and d are superior to
                                 alternative a.
    LEPAE
IpEQ/FEUP

-------
Operating  Costs
     Operating
     costs of utilities
     (million  /year)
                                    alternatives
       The operating costs decrease because the consumption of utilities is reduced when the process is heat integrated.
   LEPAE
IPEQ/FEUP

-------
Capital Investment
         The capital investment increases when the process is more heat integrated due to additional piping
                         system and heat exchangers.
LEPAE
                                                     IPEQ/FEUP

-------
Economic Potential
     For the EP alternative b has the largest economic potential and alternative a has the lowest economic potential.
LEPAE
                                                  IPEQ/FEUP

-------
Conclusions

                            [

-------
Conclusions
           As for the economics, the operating costs
           integration increases.
                                              ease as the level of energy
           However,  the capital  costs increase  with  an  increase  in energy
           integration, so that with these  trade-offs an intermediate  amount of
           enerj?v integration nroduces the mrkc^ f»/»r»nr»mi/»aii»7 VmnAfi/tiai r\r*rt/>Acc fr»**
           The design option which exchanges a large amount of heat between the
           reactor effluent and feed is superior to other designs in both analyses
           because of large energy savings that reduce operating costs and potential
           environmental impacts.
LEPAE
                                                                    IPEQ/FEUP

-------
DEQ/FEUF3

-------
 Beyond the Molecular Frontier:
  Challenges for Chemistry and
    Chemical Engineering —
An Overview of the Recent NRC
            Report
     Thomas W. Chapman, Ph.D.
     National Science Foundation
       Arlington, VA, USA

-------
The U.S. National Research Council has just published
a detailed study that summarizes the current status of
the chemical sciences.   The  report assesses  current
trends and identifies key opportunities and challenges
for the 21st  Century.  In particular, the report lists a
number of Grand Challenges for the chemical-science
enterprise and deals explicitly with a number of issues
of great relevance and concern to modern society.

This report  was supported  in part by the National
Science Foundation. This presentation will provide a
brief summary of the report  and comment on some of
the Grand Challenges as they relate to  the Pilot Project
objectives.

-------
      PROGRAMME ON SUSTAINABLE
INDUSTRIAL DEVELOPMENT IN LITHUANIA
           Prof. hab. dr. Jurgis Staniskis
       Institute of Environmental Engineering
         Kaunas University of Technology
   K. Donelaicio 20, Kaunas, tel: 300760, fax: 209372
           e-mail: Jurgis.Staniskis@ktu.lt

-------
      MAIN SUSTAINABLE INDUSTRIAL
      DEVELOPMENT MEASURES
> Cleaner production
> Quality and environmental management systems
> Product related measures
> Sustainability reporting

-------
   OBJECTIVES OF THE PROGRAMME
>   To increase competitiveness of Lithuanian industry
>   To reduce negative process and product impact to the
    environment
>   To use energy and natural resources more rationally
>   To improve working conditions and promote
    establishment of new working places

-------
 SHORT-TERM TARGETS
To achieve that at least 200 companies implement certified
environmental management systems and at least 500 companies
implement certified quality management systems (until the end of
2006)
To achieve that more than 30% of Lithuanian companies
systematically apply cleaner production approach (until the end of
2006)
To build capacity and infrastructure in the areas of eco-design and life
cycle assessment (until the end of 2005)
To build capacity and infrastructure in the area of sustainability
reporting (until the end of 2005)
To achieve that more than 10% major Lithuanian companies start
development of sustainability reports in accordance to developed
methodology (until the end of 2006)

-------
   LONG-TERM TARGETS
Jt  To achieve that majority of Lithuanian companies
   systematically apply principles of sustainable industrial
   development (until 2015)
•  To achieve performance level of industry, set after analysis
   of performance of enterprises in Lithuania and more
   developed countries (until 2015)

-------
   KEY ELEMENTS OF THE PROGRAMME (1)
1.   Establishment of framework conditions promoting
    implementation of sustainable industrial development
    measures in industrial enterprises:
       Regulatory measures
       Economic measures
       Informational measures and strengthening co-
       operation among different stakeholders

-------
   KEY ELEMENTS OF THE PROGRAMME (2)
2.    Capacity building and support to enterprises in
     implementing sustainable industrial development
     measures:
       Training programmes and development of training
       materials
       Financing of investments in cleaner technologies
       Technical assistance to enterprises

3.    Research and Development:
       Effective co-operation between enterprises and
       research organisations
       Governmental support for applied research activities

-------
     NATO CCMS Pilot Study on Clean Products and Processes
Clean Products & Processes Update
           University of Natal
Chris Buckley
Pollution Research Group
University of Natal
Durban, 4041
South Africa

-------
Group Vision
The support of sustainable development through the
promotion of Cleaner Production using process
engineering tools.

Mission Statement
To promote the effective use of water through
research, education and development

Partners
Industry, regulators and the community

-------
 Outline
process impacts and improvements
waste minimisation
process integration
             ,d con
     nstration proje
concentrates and residues
sustainable water and sanitatio
 ommunity issues

-------
Process Impacts and Improvements
LCA comparison of membrane and conventional
processes for the production of potable water
LCA of pulp and paper manufacture
LCA of a secondary water recycling system
development of a salinity LCA category
fate modelling of oxygenates in South Africa
eco-labelling of textile products
 core System for the selection of chemicals

-------
Overall Materials and Energy Used
       (per Kilolitre of Water)
       Mass
          Energy
            (MJ)
    convention
emora
onvennonai  memora
                                        0.000

-------
  Electricity Consumption
 rocess
onsumptio
  (kWh/day)
zonation
        490
edimentation
 ration
        230
  imentation
         2§E
 emical addn

-------
       Scope of Recycled Water LCA
The human modified terrestrial water pathway
  Abstraction of
   raw water
DislnbutiDn ul"
 11 Lulled
or
              VUlll'J
                           iii: used
                          water
                o
           used water
                                                       SLlJ U) SIM
      water Quality issues


SallHJlV
Study



LCA eomp.iiisiMi sl;jdji.'s
• provision of secondary water
• flllue:!! JISLJJUI.HL-



-------
           Score System
Purpose
 - grading of organic textile chemicals and dyestuffs
from an environmental perspective
Reason
 - many products of unknown composition
 - difficult to analyse the effluent
Co-regulatory approach

-------
Basis of the Score System
    exposure (A x B x C)
    - mass to drain (A)
    - biodegradability (B)
    - bioaccumualtion (C)
    - toxicity (D)
    score range from 1 to 4 on a log scale

-------
          Typical  Score Report
O
     64
     56
     48
   < 40
   £ 32
     24
     i6
      8
      0
                    Toxic
                    Section
                             High Priority
      	1	3
      Non/Low  i::::::::::::::::::::::*.
      I X^XX|X%         jl
      IOXIC         1
      o 0 ct i o n
            1
                  2         3
                   Toxicity (fish)
ccc

-------
  Waste Minimisation Clubs
group of enterprises (5 to 20)
subscriptions
regular facilitated meetings
training
group learning
member to member support
environmental and economic focus

-------
Waste Minimisation Clubs - Savings
                   raw material
             recycle   3%
               9%
        technology,
         16%
                            Housekeeping

                              72%

-------
     Metal Finishing Club

29 members - 15 active
More than 50% had <50 employees
Over 60% were jobbing shops
Bimonthly meetings
Site visits
Training for Project Champions

-------
       Results - MF Club
Item
Water and effluent
Chemicals and metals
Energy
Carbon dioxide
Sulphur dioxide
Nitrous oxide
Total
Cost Saving in
US$/vear
58954
194355
45775
N/a
N/a
N/a
298 724
Environmental Saving / year
149 000 kl
112 tons (for 5 companies)
16 000 MWh
1 400 tons
13 tons
6 tons
N/a
Note: N/a = not applicable
    A conversion rate of US$ 1 to R 7 was used in this table.

-------
  Process Integration - Pine
                             nomic
a systematic method of optimising the allocation
of water to the hierarchy of uses that typically
occur in an industrial system
Accounts for all te '
environmental constraints that
processes involve
 roperly carried out, it will provide an impartial and
transparent assessment of water and effluent
requirements

-------
Typical Water Use Circuit

•» PKOCLyai p *

RAW L . , pp^isMi fc WAS1L- .
.^Tr> HL4 IvILN ft 9 rrej^caD-. p ,,M,™,1" 1
• V. <. L. IT.



1 	 }J PHOCLSS3 j 	 »
J I
BRAT { XSlud STftM CO NO LOSS
HHLAIN'LNI 	 •-* SYSra^l

L
ION EXCHANGE REGEN.
h 1 COOLING TOWER fc
j iJLOliVJOWN

OONTAMINATED
STORM WATER
WAJiFLWA 1 LR LJISC'-ARj'
IHUi.ir'/LNl *

-------
     Pinch Applications
water cooled thermal power station (Mathlab)
chlor-alkali plant (hand, WaterPinch, GAMS)
amino acid plant (WaterPinch)
pesticide manufacturer (hand^
pulp mill B (WaterPinc,,
pulp mill C (WaterPinch)
oil refinery (Aspen)
textile mill (hand)
food and beverage plants (hanclx

-------
Modelling, Control and Optimisation
chlorine dose of conditioning reservoir
(CFD/MINLP)
ozone contactor (CFD - Fluent)
 iquaduct energy (MIN
cooling system chemistry (Minteqa2)
cooling system control (WEST)
anaerobic system

-------
    CP Demonstration Projects
textiles (Danced / Danida)
metal finishing (Danced / Danida)

-------
 Concentrates and Residues
dye concentrates - anaerobic digestion
toxicity and biodegradability assays
landfill leachates
acid mine drain
high value (inorganic + hydrocarbon) products
barium process
electrochemical processes
sonochemistry

-------
      Water and Sanitation
anaerobic membrane bioreactor
sustainable engineering of free basic water

-------
               Policy
receiving water quality standards (industry)
National Waste Management Strategy (waste
minimisation)
National Innovation Strategy (cleaner production)
UNEP (WSSD Regional Industrial Report - Africa)
UNIDO (Environment and Industrialisation in
Sub-Saharan Africa)
Minister's Water Advisory Council

-------
        Staffing

8 researchers
8 PhD students
25 masters students

-------
      Community Issues
refinery comparison
CP foresight proposal
energy integration

-------

-------

-------
              )Ucation:  Textile Processin
Water Using Operations (recipe dependent):
• Scour, Bleach, Dye, Rinse, Soap, Soften;
• Cooling water;
• Printer belt washing;
• Machine cleaning

Water Using Operations (recipe independent):
• Treatment operations (backwash, reagent mixing);
• Cooling tower makeup;
• Factory cleaning;
• Ash / coal wetting;
• Boiler makeup

-------
      lication: Polyester
In operation in Denmark for 2 years
Savings:
     Water: 40 - 80 litres per kg fabric
          25% - 50%
     Steam: 4 - 6 kg steam per kg fabric
          20% - 30%
     Chemicals: negligible

-------
                 lication: Cotton  Knitwear
Pre-dyebath:
Post-dyebath:
      90
      i Bleach!
        W
        I

      |80
        HR
      1100%
      |20
       CR
      1100%
      80
       Neut.
 Water: 20 - 40 litres per kg fabric
       up to 30%
 Steam: 1 - 2 kg steam per kg fabric
      180
        Dye m*m
      1100%

      20~
        CR
      100%
       80
        lip •VAVJ

       100%
                                      80
                                      Neut. !
                                     1100%
      120
       Soften mgem
      1100%

-------
                        lication: Acrvlic
 Scour
 100%
20
 Dye
100%
190
 Q p
1100%
 OR
1100% I
 Qp
100%
-^100
o
0>9°
0) Qri,
•o 80
0,70
= 60
250
0)
Q. 40
| 30
20
10
Drain Store 1 Store 2 Store 3
•*«** 1
.* '. T.= T,= T,=
58°C 32°C 27°C
*
* ^1
»
*.
4^
* » » « «


0 '
00:00:00 00:07:12 00:14:24 00:21:36 00:28:
time (hh:mr
Stop rinse







* *



48 00:36:00 00:43:12 00:50:24
n:ss)
                         50li,
                     30% - 40%
               Steam: negligible
Chemicals: 10% of softener

-------

-------

-------

-------
                                Capital Costs
Economic considerations:
 a. 17% POR, 1 year ammortisation
 b. piping, valves, monitoring equipment, tanks.
Capital cost: R 0.5 mil - 1.2 mil
Payback period: 6-18 months

-------
     Sixth NATO CCMS Pilot Study
    on Clean Products and Processes
Ionic Liquids; Research and Application
             Jim Swindall
         Cetraro, Italy 11 - 15th May 2003

-------
    Which  Industry  is the Dirtiest?
By-products as a proportion of production for the chemical
        Industry
       Oil refining
     Bulk chemicals
     Fine chemicals
     Pharmaceuticals
Production /
 tons p.a.
  106- 108
    4   6
  10 - 10
  102- 104
  10 - 10
E-factor
  0.1
  1-5
 5-50
25-100
                        R.A. Sheldon, in "Precision
                        Process Technology " (eds.
                        M.P.C. Weijen andA.A.H.
                         Drinkenburg), Kluwer,
                         Dordrecht. 1993. n. 125
                              ' ,1 ' ;

-------
Some of the Major Problems
> Old, inefficient processes
> Solid waste
> Heavy metals
> Unnecessary process steps
> Solvent waste

-------
    Alternative Solvents
*No solvent (Heterogeneous catalysis)
* Water
* Supercritical Fluids
•Monic Liquids

-------
Neoteric (New) Solvents
      Breaking new ground!
 Supercritical fluids
 Ionic liquids

-------
   What are ionic liquids ?
They are salts (composed only of ions)

They are molten at or near ambient
temperatures (m.pt. < 100 °C)
   Solvent
               Heat
                  0 ©0^0
                  0©0©©
 Ionic Solution
                    Ionic Liquid
                                           ! ,1' ,

-------
Room-Temperature Ionic Liquids
             Important Properties
 Liquid range of 300 °C (-96 - +200 °C)
 Excellent solvents for organic, inorganic and
 polymeric materials
 Acidic compositions are superacids (pKa « -
 Some are very water sensitive and must be
used in a dry box; others are hydrophobic and
air stable
 Thermally stable under conditions up to 200
°C
 NOW -  easy to buy and simple to prepare

-------
Room-Temperature Ionic Liquids
       Why solvents for GREEN synthesis?
* NO measurable vapour pressure
* Exhibit Brensted, Lewis, Franklin and "super"
  acidity
* HIGHLY solvating - therefore low volumes used
*t* Catalysts as well as solvents
* Highly selective reactions
* NEW CHEMISTRY

-------
         Ionic Liquids
Designer Solvents
(1018 ionic liquids are feasible)
New paradigm
New chemistry
No VOCs
Recyclable
Cost effective
Scale-up

-------
Are Ionic Liquids Toxic ?
The University of Bremen have an extensive
programme on ionic liquid toxicity
Initial studies (Green Chemistry, April 2003) are
very encouraging, as results indicate low toxicity,
reasonable biodegradability and low eco-toxicity
Long aromatic side chains should be avoided

-------
SOURCES OF IONIC LIQUIDS
                      'dliient
  A I • I mtm A • i • i
  w i •• • • • i ••
                           ! ,1 ' ,

-------
   Other Sources
       ,MERCK
                 SACHEM
These, too, are primary sources of supply
                        + + - w*

-------
    Green  Industrial
    Applications of
      Ionic Liquids
            Edited by
Robin D. Rogers, Kenneth R. Seddon
       and Sergei Volkov
         NATO Science Series
   Mathematics, Physics and Chemistry

-------

      ACS SYMPOSIUM SfRltS 818
   Ionic liquids
   idustrial Applications
   to Green Chemistry
             . -  ..-•


         EDITED BY
Robin 0. Rogers and Kenneth R. Seddon
Now Published
                                 33 Chapters
                                 State of the Art in 2001

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          (vk)WILEY-VCH
Ionic Liquids
in Synthesis
Peter Wasserscheid, Tom Welton (Eds.)
Now Published


8 Chapters


Comprehensive
overview up to 2002

-------
Ionic Liquid Publications
  500
  450
  400
  350 -
1
  300 _
  250 _
  200
  150
  100
  50
    O
1995
            •  •
1996
1997
1998
1999
                      2000
                         2001
2002

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Recent IL meetings

    VtAume 4 Number I
    fcbnury 1M1
     r.
Boston ACS Autumn Meeting; 18th-
22nd August (the sequel to San
Diego) - ten sessions (more than 60
lectures) on ILs

    http://bama.ua.edu/-rdrogers/Bo
ston/
               Green Solvents for Catalysis
               (Bruchsal, Germany,  13th-16th
               October)

<|KMH
                            w<
                  +   -   +

-------
  Forthcoming IL  meetings
New York ACS Autumn Meeting; 7th-11th September,
2003 (the sequel to Boston) - ten sessions (more than 60
lectures) on ILs

NATO ASI Summer School (Pisa, Italy, 18th-30th April,
2004)
Green Solvents for Synthesis (Bruchsal, Germany, 3rd-6th
October, 2004)

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Industry/University Co-operation
       Queen's
       University
       Ionic
       Liquid
       Laboratories

-------
QUILL Members
^Avecia
>BNFL
>ChemVite
>DuPont
> Strata
> Merck
>SASOL
>Cytec
UK
UK
UK
UK
UK
UK
SA
Canada

-------
           QUILL Members
^Chevron
>SACHEM
>UOP
^Eastman
>C-Tri
> Sobering Plough
> Shell
>Novartis
-USA
-USA
-USA
-USA
-USA
- South Korea
-Rol
-NL
- Switzerland
18 members from 9 countries on 4 continents

-------
QUILL IAB with QUILL Research Team

            ..•
                          '
                              .


-------
••••I


-------
QUILL is a Marie Curie Centre
  Hie European Commission
           Marie Curie Fellowship;
                                   ! ,i',

-------
European Network of Excellence
               ILIAD
    Ionic Liquids: Implementation And Design
314 researchers
177 postgraduate students
77 partners
21 countries
5 major industries
7SMEs
€23,500,000

-------
  European Network of
        Excellence
           ILIAD
Ionic Liquids: Implementation And Design
 If you want to be included, it is still possible
   Contact our Network Administrator at:
               h.anderson@qub.ac.uk
              Dr. Heather Anderson

-------
  European Network of
        Excellence
           ILIAD
Ionic Liquids: Implementation And Design
 If you want to be included, it is still possible!
  Contact our Network Administrator at:
    h.anderson@qub.ac.uk
              Dr. Heather Anderson

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Can Ionic Liquids be Used on an
       Industrial Scale ?

-------
   Institut Francais du Petrole
                Process
> Biphasic catalytic process (Difasol)
> Dimerisation of butenes into a mixture of
  low-branched octenes
> [bmim] [Al2Et2Cl5] used as solvent and Lewis
  acid with a nickel(II) catalyst
> Pilot plant stage for some years
> Available for licensing but not
  commercialised
  (bmim = l-butyl-3-methylimidazolium

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BASF Process
              BASF

-------
       BASF  BASIL Process
  Biphasic Acid Scavenging utilizing Ionic Liquids
The process is a multi-ton process, and has been
running in Ludwigshafen (Germany) for over one year
1 -Methylimidazole (mim) is used to scavenge produced
HC1, forming liquid [Hmim]Cl (m.pt. 75 °C)
Almost five years since the announcement in C&E
News of the potential of ionic liquids

-------
BASIL Process
  ROM
    N
\
     recycle
              pure liquid product
              ionic liquid
              Cl
                   N
H

-------
The BASF Team
                     The BASIL team
                     (from the left):
                     Mr. Rudiger
                     Biittner, Mr.
                     Holger Ganz, and
                     Dr. Matthias
                     Maase

-------
BASIL Process
The [HmimJCl formed is a dense
liquid, it is separated by gravity, and
then the        1 -methylimidazole
released and recycled
This BASIL process is used for the

alkoxyphenylphosphines, by treating
chlorophenylphosphines with
alcohols, liberating HC1
The products are used as precursors
for the synthesis of photoinitiators
that are used in the manufacture of
printing inks as well as glass fibre

-------
 Other reactions for the BASIL
              Process
> Esterifications (with acid chlorides)
> Silylations (with chlorosilanes)
> Phosphorylations
> Sulfuylations
> Eliminations (of HX)
> Deprotonations (e.g. to form ylids)
>And so on

-------
         Implications
This industrial application has
demonstrated for the first time that ionic
liquids can be handled, pumped and
recycled economically, on a multi-ton
scale, and with ease

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  SOME CASE STUDIES ON CLEAN PRODUCTS AND PROCESSES.

  David Wolf* and Chaim Forgacs**

  *Department  of Chemical  Engineering,  Ben-Gurion University, Beer-Sheva,Israel and
Department  of  Chemical  Engineering and Biotechnology,The College of Judea and
Samaria, Ariel,Israel.
  **Department of Environmental Engineering, Ben-Gurion University, Beer-Sheva, Israel.

   1. Water Desalination.
   Due to the lack of sufficient water resources in Israel it was decided to rely on Sea
Water  Desalination as an additional source of potable water. The plants in  consideration
are very large in the range of 50 million cubic meter of water per year per plant.
   While the technologies involved are available in Israel due to extensive R&D of these
technologies,  the problems that  are  now dealt with are  related to  the  environmental
aspects.
   These refer to the effect of salty water on aquifers which has to be  avoided  and the
effect of highly salted  reject of the desalination plant on the environment of the sea area
where it is introduced.
   The design of the  plants takes into account the above problems as well as the location
of the plant which in itself is a problem to be considered.

   2.Water treatment.
   Recently a ministerial order of the Ministry of the Environment was issued stating that
the industrial waste especially from the petrochemical industry in the Haifa Bay
   Waste could not be sent to the river without pre treatment of the streams to the level
that it could be  released to the environment. In fact several options were considered for
disposal and it was concluded that even the treated waste water could not be returned to
the river and instead should be sent by a pipe deep into the sea.
   Same of the companies have already  spent the necessary funds  in order to comply
with the demand and  others are in the process of implementation of the above mentioned
order.
   We hope that the next step will be of adaptation of the processes and  indeed  of
changing the processes so as to take into account their environmental impact.

-------
   3. Oil spills cleaning.
   The golf of Eilat and Akaba is used by the neighboring countries Israel and Jordan for
transportation of oil tankers and pumping stations of the oil to their respective Countries.
   In order to preserve the environment and its rich  marine life a ship was acquired  in
order to clean the water from oil whenever necessary.
   The ship was built by a Norwegian company and is now operating in the golf. The ship
has the necessary equipment in order to fulfil the required tasks.

   4.Rotem Amphert
   Rotem Amphert  is a  large chemical industrial complex located in  the Negev desert,
specializing mainly in the production of phosphate fertilizers and phosphoric acid. Recently
they have developed a new process to convert "green" phosphoric acid to "white" (pure)
phosphoric acid.
   The novelty of the process is that it has no waste stream at all, and  still less expensive
that the one formerly used. It is a good  example to show, that it is possible to improve
processes in  the chemical industry which are environmentally more friendly, and at the
same time economically attractive

   S.Ramat Chovav
   Ramat Chovav is a large industrial park in the Negev desert, about  10 kilometers from
Beer-Sheva, where  polluting chemical industries are concentrated. The  national  site for
hazardous wastes is located here, too. A couple of years ago, a centralized system for
industrial waste disposal was erected. In the last year a novel biological treatment plant
was introduced to treat most of the industrial waste of the complex.

   6.Replacement of Hg by membranes in electrolysis of NaCI.
   The  production of chlorine and  NaOH in the electrochemical process was normally
done by the  electrolysis of sodium  chloride with Hg  electrodes. Due to the poisonous
characteristics of Hg and due to fear of catastrophic accidents the electrodes are now
replaced by membranes  thus eliminating the  environmental effects and  also reducing
contamination problems by traces of Hg.in other products of the  plants.

   7. Improvements In Fuel Cells Performance.

-------
  One of the promising sources of "pollution free" electricity is the fuel cell which efficiently
converts chemical energy to electrical energy. E. Korin and A. Bathelheim (Dept. of Chem.
Eng., Ben-Gurion University) have studied the electrocatalysis  of oxygen reduction at the
cathode, the electrocatalysis of methanol at the anode and the mass transport through the
electrolyte membrane. They added a special coating to the cathode that is a barrier to the
methanol but is  permeable to the oxygen. This they  did in order to avoid the methanol
crossover from the anode to the cathode which has detrimental  effects on the cathode and
on the efficiency of the process. The coating consists of an inner polymeric film which is a
good proton conductor and an outer film which is obtained by elecropolymerization of a
monomeric macrocyclic compound.
  This avoids almost completely the methanol from reaching the cathode.

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    Process Intensification in
         European Union:
 Current Work and Future Plans

             G.P. Gallios
 Aristotle University of Thessaloniki
         School of Chemistry,
Lab. Gen. & Inorg. Chemical Technology
         Thessaloniki, Greece
     George Gallios, Aristotle University of Thessaloniki,
              Email: gallios@chem.auth.gr

-------
S
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•  About Process Intensification
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         a Definition


         a Barriers


         Current work in EU
IO
  Future plans in EU

  Current situation in Greece
       George Gallios, Aristotle University of Thessaloniki,

                 Email: gallios@chem.auth.gr

-------
o
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s    Process Intensification  (PI)
2
      -  a highly inovative concept
        (a design philosophy)
§     •  refers to technologies and strategies that
        enable the physical sizes of con ventional
        process engineering unit operations to be
        significantly reduced
                   In other words
        a smaller compact piece of equipment
        takes the place of a larger one at the
g       same given capacity or mass flowrate
      George Gallios, Aristotle University of Thessaloniki,
                Email: gallios@chem.auth.gr

-------
s    PI Benefits
o
O
      • Size reduction (factor 3 to 4)
      • Cost reduction due to less
x        a Support structure
         a Column foundations
         a Pipe runs
      • Less Pollution to Environment
      George Gallios, Aristotle University of Thessaloniki,
                 Email: gallios@chem.auth.gr

-------
£
g    PI Barters
O
CM
s
o     High risk technique for potentially high gains
      Concerns about the cost of additional
      hardware.
      The need for more flexible process integration
      design tools and cost-effective heat exchange
      equipment.
g   • Lack of understanding about the technique in
^     many industries.
       George Gallios, Aristotle University of Thessaloniki,
                 Email: gallios@chem.auth.gr

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PI Barters (con.)
 The impact of change on plant reliability,
 flexibility and maintenance.
 The risk of disturbances to production.
 The long payback in some applications.
 The (possible) need for new plant.
 Concerns about the scale-up from
 laboratory/pilot trials to full-scale production.
       George Gallios, Aristotle University of Thessaloniki,
                 Email: gallios@chem.auth.gr

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PI - Operational projects

 There are currently only two known Process
 Intensification projects operational in the
 European Union (UK, Germany) and it is too
 early to comment on their success.
      George Gallios, Aristotle University of Thessaloniki,
                Email: gallios@chem.auth.gr

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      Hnlriirvg tank
         pumps 3
        lanh
         PI in effluent treatment
         (wet oxidation process)

             Unintensified
        Total cost: 2.4 M ECU
Cost Gwews ct process fltensrlkaticr. in effii
                                        Intensified
                                 Elflucuil
                               HoW«ng tank
                                  pumpG x 2
                                   High
                                   transler
                                   pumps
                                              Ellluenl
                                         Effluent cooler
                                       Total cost: 0.9 M ECU
                                           (62% less)
        George Gallios, Aristotle University of Thessaloniki,
                    Email: gallios@chem.auth.gr

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Process Integration - Process
          In tensifica tion

   RTD - Current Work in EU \
    mum
    UK
    Work on catalytic reactors
     a Modelling, design and RTD activities
    Funding: Government & Industry
     a 3 years - 4.5 MECU
      George Gallios, Aristotle University of Thessaloniki,
               Email: gallios@chem.auth.gr

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Food & Diary installations (widely)
aluminium and metal installations (minor
extend)
Refinery (Installed Mass & heat control)
Funding: Industry (mostly) & Government
Applied RTD participants
 a Industry, R&D institutes, Universities and
   Government
       George Gallios, Aristotle University of Thessaloniki,
                  Email: gallios@chem.auth.gr

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Development of energy analysis tools.
 a optimisation of different tools
 a  commercialisation of PI study tools
 a exchange of knowledge and experiences
   (Internet - workshops)
Participants
 a process industry, consultants,
   RTD institutes, universities and
   SME organisations
Funding: 0.5 MECU
       George Gallios, Aristotle University of Thessaloniki,
                   Email: gallios@chem.auth.gr

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Pinch and exergy analysis
 a chemical industry
    S PRODET programme
    S 1,5 year-33 kECU
 a and textile industry
    S Grupo National de Integracao de Processes
    S l year-13 kECU
        George Gallios, Aristotle University of Thessaloniki,
                     Email: gallios@chem.auth.gr

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s
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Process Integration - Process
          In tensifica tion
    RTD - Future Plans in EU
    I • Process Integration is used successfully in
       certain industries
•     • Needs:
        a Development of robust methods in batch
          processes
        a Minimisation of water consumption and waste
      George Gallios, Aristotle University of Thessaloniki,
                Email: gallios@chem.auth.gr

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• Priorities:
   a Improved analysis tools and data collection
     methods
   a Better recovery of waste heat, heat storage
     and the incorporation of heat pumps
   a Encourage the use of PI tools by smaller
     companies and by industries
   a Wider dissemination of existing case study
     material and more case studies
       George Gallios, Aristotle University of Thessaloniki,
                   Email: gallios@chem.auth.gr

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• Basic RTD, prototyping and component
  development on reactors and separators
• Government, industry & universities will be
  involved in a 5 years programme with
  several MECU's
• Potential benefits:
   a Better yields
   a Safety
   a Reduced environmental impact
   a Energy saving
       George Gallios, Aristotle University of Thessaloniki,
                 Email: gallios@chem.auth.gr

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• • Industry, R&D Institutes, Universities and
    Government should work together on PI
  • Potential benefits:
    a Energy saving
    a Improved product quality
    a Competitiveness and environmental
      protection
       George Gallios, Aristotle University of Thessaloniki,
                  Email: gallios@chem.auth.gr

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• •  Stimulate market penetration:
    a exchange of experiences (panels)
    a promote wider applicability of PI tools
• •  Work should be done by:
    a  Industries, including SME and
      governmental agencies
  •  Budget needed: 0.5 MECU
• •  Potential benefits:
    a process innovations
       George Gallios, Aristotle University of Thessaloniki,
                 Email: gallios@chem.auth.gr

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^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^
^^^^^^^^^^^^^^^^^^^^^^


I • Promote PI in various sectors
m • Potent/a/ benefits:
•• a Ceramics
m a Petrochemical industry etc.


















George Gallios, Aristotle University of Thessaloniki,
Email: gallios@chem.auth.gr

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Greece - Current status
  Most of the work is on:
   a Membrane Processes
   a Reverse Osmosis (RO)
      George Gallios, Aristotle University of Thessaloniki,
                Email: gallios@chem.auth.gr

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0)
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        a special membranes and transport
_w-   u    processes through human skin for
         transdermal drug delivery systems
      George Gallios, Aristotle University of Thessaloniki,
                Email: gallios@chem.auth.gr

-------
£
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             ^ micro filtration
£>   I        v' reverse osmosis
      George Gallios, Aristotle University of Thessaloniki,
                Email: gallios@chem.auth.gr

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£
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O
     Greece - Membrane Processes
       a Fouling (by CaSO4) ofRO mem-
w-   B     branes in a desalination process
          > Model Production
IO

       a /?0 plant driven by wind energy
8"  "
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      George Gallios, Aristotle University of Thessaloniki,
               Email: gallios@chem.auth.gr

-------
£
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5   " - LIFE (EU) & Govenrnment (GR):
o   I   a Recycling waste water from a milk
          collection station
           > Techniques:
**            v con ventional filtration
        s ultra filtration
        ^ reverse osmosis
      George Gallios, Aristotle University of Thessaloniki,
                Email: gallios@chem.auth.gr

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     Greece - Membrane Processes
«   • Brite-Eyram (EU) :
      a Ceramic and carbon microporous
        membranes for: CO2/N2, CH4/C2H6,
        pollutants separation with oil refining
        processes and removal of VOCs from air
        (streams
      a Mesoporous (e.g. Vycor) and polymer
        membranes, after plasma treatment
        formation of selective thin top layers
        with microporous structure
      George Gallios, Aristotle University of Thessaloniki,
               Email: gallios@chem.auth.gr

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     Greece - Membrane Processes
JOULE (EU):
 a Optimisation and evaluation of
  inorganic use of membranes in
  e.g. oil refining processes
JOULE - THERMIE (EU) :
 a Enhanced oil recovery methods
  using expertise on flows through
  porous media
      George Gallios, Aristotle University of Thessaloniki,
               Email: gallios@chem.auth.gr

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         George Gallios, Aristotle University of Thessaloniki,

                        Email: gallios@chem.auth.gr

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Wettability Determination as an Important
   Factor in Design and Environmental
Performance of Some Industrial Processes
             Andrzej  Doniec

 Pollution Prevention Center at the Technical University of
                Lodz (Poland)

-------
Wettability is a phenomenon manifesting
    itself within a three-phase system
           gas (air)
                   \ solid surface
gas (air)
                     |jquid
                     liquid 2

-------
 Many industrial processes are particularly
    associated with wetting phenomena

heat transfer processes (heat exchange, steam
condensation)
some separation processes (absorption, distillation,
floatation)
coating processes (electroplating, painting,
printing)
specific processes of environmental technology
(wet dust removal from exhausted gases, cleaning
of open surface waters after oil spills etc.)

-------
  Wetting of solid surface with a liquid flowing
              down a vertical plane


                                            I
                                            I
rivulets, drops, dry spots
                    uniform film
wavy film

-------
Considering wetting action in a three-phase
 system one can differentiate two opposed
                  cases
      thorough wetting and lack of it

      These are resulting in
      •liquid films
      •ball shaped drops

-------
Highly efficient industrial processes produce
         fewer emissions and waste
 Numerous industrial processes proceed with an
 interfacial area generation
 Generating and maintenance films or droplets
 dimensions (thickness and diameter) is a
 fundamental task for effective run of the process

-------
Important measure of wettability is contact angle
                                     The angle 0
                                     measured at the
                                     point of contact of
                                     three phases
                                     forming the given
                                     system

-------
                    Light source
Sessile drop

-------
Image processing
Input approx. (initial)
contact angle value
Drop shape equation
Contact angle
Compare recorded and
calculated drop profile
Successive approximations

-------
A comparison of a recorded drop shape and a
              calculated one
                               x, mm

-------
Liquid rivulet flowing down a vertical plane
  I
                            The minimum rivulet
                            corresponds with the
                            liquid flow rate value
                            below of which single
                            drops slide down the solid
                            surface

-------
   Liquid film and minimum rivulet thickness
             6 = 1,45
                           5
(1 - cos 9)5
t
8

1
         5 -- film thickness
         r| - - viscosity
         o-- surface tension
         p -- density
         g -- acceleration of gravity
         9 - contact angle

-------
Theoretical values of minimal rivulet dimensions
          Selected liquids  Temp. 20 °C
Liquid
Glycerol
Ethylene glycol
Water
Ethanol
Contact angle
degree
5
90
5
90
5
90
5
90
Thickness
mm
1.78
5.42
0.322
0.982
0.113
0.345
0.111
0.337
Width
mm
60.7
5.6
11
1
3.86
0.36
3.78
0.345

-------
Liquid film composed of rectangular segment
    and two halves of a minimum rivulet

-------
          Langmuire's technique
                             Laser beam directed to
                             a rivulet edge
laser beem
                             When incidence and
                             reflection angles are equal
                             one can determine a value
                             of contact angle

-------
 Equilibrium and effective (minimum rivulet)
             contact angle values
    Material
                          Contact angle
                   equilibrium
                     degree
              effective
                degree
Aluminum
 69
18
Brass
80.5
46
Stainless steel
75.5
40

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             Liquid film stability
Liquid surface disturbance






















                                      Waves on the liquid
                                      surface are not the
                                      sufficient condition
                                      to break down the
                                      film
                                      Somewhere solid
                                      surface must be of
                                      different energy state
Change of solid surface energy

-------
A hint for equipment (film
   distillation apparatus) prod
                          evaporators
                             ucers:
The material used for construction must be
of the highest quality
      fully energy uniform surface

-------
Development and Integration of New Processes
 for Greenhouse Gases Management  in Multi-
    Plant, Chemical Production Complexes


T. A. Hertwig, A. Xu, D. B.Ozyurt, S. Indala R.W. Pike,

       F. C. Knopf, J. R Hopper,and C. L. Yaws

           A joint industry-university research effort
            IMC Phosphates, Motiva Enterprises,
          Louisiana State University, Lamar University

   Sponsored by U. S. Environmental Protection Agency

     NATO CCMS Pilot Study on Clean Products and Processes
           2003 Annual Meeting, May 11 -15, 2003
              Hotel San Michele, Cetraro, Italy

-------
       LSU  Mineral  Processing Research  Institute
Home
Research
Emphasis
Collaboration
Computer
Programs
Research Results
Internet Courses
Text Book
Industry
Associates
Staff
Contact
                             M line rails       	
                                      arch llnsitiltiuiite
                      setpoints
                       for
                     controllers
                                               Louisiana
                       opti mat
                       operating
                       conditions
                        Mission

                        History
                        Research
                       Directions
                           Processing, economic and environmental research for the main
                           mineral of the State: oil and natural gas, and for sulfur, salt and
                           lignite.
                           Formed in 1979 as one of 31 U.S. Department of Interior State
                           Mineral Institutes.

                           Focus on minerals processing research for chemical plants and
                           petroleum refineries. Cooperative agreements are in place with IMC
                           Agrico, Monsanto, and Motiva (formerly Star/Texaco).
All  of the information  given in this presentation is available at
                              www.mpri.lsu.edu

-------
                     Background

      Pollution prevention
      -  was an environmental issue
      -  now a critical business opportunity

      Long term cost of ownership must be evaluated with
      short term cash flows

Companies undergoing  difficult institutional transformations
Emphasis on pollution prevention has broadened to include
            Total (full) cost accounting
            Life cycle assessment
            Sustainable development
            Eco-efficiency (economic and ecological)

-------
     Broader Assessment of Current and Future Manufacturing
                       in the Chemical Industry

Driving forces
       ISO 14000,
        "the polluter pays principle"
       Anticipated next round of Federal regulations associated with global
       warming
       Sustainable development

Sustainable development
       Concept that development should meet the needs of the present
       without sacrificing the ability of the future to meet its needs

Sustainable development costs - external costs
       Costs that are not paid directly
       Those borne by society
       Includes deterioration of the environment by pollution within compliance
       regulations.

Koyoto Protocol - annual limits on greenhouse gases proposed beginning in
2008 - 7% below 1990 levels for U.S.

-------
            Overview of Presentation
Chemical Complex and Cogeneration Analysis System
     for multi-plant chemical production complexes
Advanced Process Analysis System
     for operating plants

-------
Chemical Complex and Cogeneration Analysis
                   System

Objective: To give corporate engineering groups new
          capability to design:

   - New processes for products from greenhouse
     gases

   - Energy efficient and environmentally acceptable
     plants

-------
               Introduction

Opportunities
 - Processes for conversion of greenhouse gases
  to valuable products
 - Cogeneration

Methodology
 - Chemical Complex and Cogeneration Analysis
  System
 -Application to chemical complex in the lower
  Mississippi River corridor

-------
     Related Work and Programs
Aspen Technology

Department of Energy (DOE)
 www.oit.doe.gov/bestpractice
Environmental Protection Agency (EPA)
 www.epa.gov/opptintr/greenengineering

-------
Chemical Complex and Cogeneration Analysis System
      Chemical Complex Analysis System
         Determines the best configuration of plants in a
        chemical complex based on the AlChE Total Cost
        Assessment (TCA) and incorporates EPA Pollution
        Index methodology (WAR) algorithm


       Cogeneration Analysis System
        Determines the best energy use based on
        economics, energy efficiency, regulatory emissions
        and environmental impacts from greenhouse gas
        emissions.

-------
                      Structure  of the  System
                            Graphical User Interface
ComplexFlowsheet (Input)
• Process flowsheet for plants in
complex and connections
• Process Simulation - material
and energy balances, rate
equations, equilibrium  relations,
physical and thermodynamic
properties,
• Profit function prices, economic,
environmental and sustainable
costs
• Steam and other utility
requirements
• Utility costing
               Database
                                                 Optimum Complex Configuration
                                                 and Energy Use (Output)
                                                 • Optimal profit and configuration
                                                 presented in tables and on the complex
                                                 flowsheet
                                                 • Identification of optimal cogeneration
                                                 structure, new processes for greenhouse
                                                 gases and nanotechnology
                                                 • Sensitivity analysis for costs, raw
                                                 materials, demand for products, operating
                                                 conditions.
                                                 • Utilities integrated with plants
                                                 • Turbine and HRSG performance
                                                 • Utilities Costing and Profitability
                                                 for different operation conditions
Total Cost Assessment
Product prices, manufacturing,
environmental and sustainability
costs
                           Mixed Integer Non-
                           Linear Program Solver
                           Simulation equations for
                           individual plants and
                           connections
Sequential Layer Analysis for
Cogeneration
• Each plant's current energy use
   -Cost effective improvements
   (Heat exchanger network analysis)
   -Cogeneration option
• Corporate energy use in multiple plants
• Cogeneration systems for chemical complex
• State wide analysis
   - Impact of merchant power plants
   - Emission reductions

-------
           AlChE Total Cost Assessment
Includes five types of costs: I direct, II overhead, III liability,
     IV internal intangible, V external (borne by society -
     sustainable)

 Sustainable costs are costs to society from damage to the
     environment caused by emissions within regulations, e.g.,
     sulfur dioxide 4.0 Ib per ton of sulfuric acid produced

 Environmental costs - compliance, fines, 20% of manufacturing
     costs

 Combined five TCA costs into economic, environmental and
     sustainable costs

     economic - raw materials, utilities, etc

     environmental - 67% of raw materials

     sustainable - estimated from sources

-------
Illustration of Input to the System for Unit Data

-------
   Typical Cogeneration Results on the CHP Diagram
Pindi 4608

 Abroach
       537 R
               946 TC
                   892 R
                          1634R
919R
_^
Stack
gas
.69(5 psia
SR
HRSG
rt /y f.
fW\
1
Water f T Steam
420 Ib/s
j

h.

465psia
919 R


^K*Xx»1
Air
Cortp.
1^^
Air


139psia
1100 R
j
Fuel
1 -j- ,, .

_hk ,^« 1 .--« 1 	
^ C ortfc . L- ham.
126 psia
^rtSO R 1 ^^^
T^

^™ ^T_ TUA
                                                     177SR
                                                      254 MW
                       Air
                       1742 Ib/s
                       14.696psia
                       537 R

-------
     Comparison of Power Generation
                             Conventional
               Cogeneration
Operating efficiency
 33%
  77%
Heat rate
(BTU/kWh)
>10,000
5,000-6,000
NOX emission
(Ibs of NOX / MWh)

CO2 emission
(tons of CO2 / MWh)
  4.9
 1.06
  0.167
  0.30

-------
      Saint Francisville
      Crown Vantage
Port Hudson
Georgia-Pacifi

North of Baton Rou
Ferro (Grant)
Safety - Kleen (LaidlawJ
Exxon (Allied / Paxon)
Exxon Resins
Deltech (Foster Grant)
Exxon Plastics
         Port Allen
         Placid
         Exxon - Lubes
   Addis / Plaquemine
   Borden (OxyChem)
   Sid Richardson
   DSM Copolymer
   Dow
   Geon
   Air Liquide
   Air Products
Plants in the lower Mississippi  River Corridor
       Baton Rouge     St Gabriel           Geismar
       Rhodia (Stauffer)
       LaRoche (Kaiser)
       DSM (Copolymer
       Albemarle (Ethyl)
       Formosa (Allied)
       Exxon - Refinery
         xxon Chemical
                         St Gabriel
                         Air Products
                         Novartis (Ciba Geigy)
                         Ciba
                         Pioneer (Stauffer)
                         ICI
                         Zeneca
                               Carville
         lied Signal
Borden
Air Liquide
Uniroyal
Rubicon
Praxair
BASF
Shell Chem
Air Prod
Vulcan
                                                                     Sunshine Bridge & Below
Air Products
Motiva (Star/Texaco)
DuPont
OxyChem (Convent)
IMC - Agrico
Garyville
Nalco
Marathon
Epsilon
Betz (Reserve)
DuPont (LaPlace)
                               Cosmar
                               Fina
                                 Geismar
                                 Allied
                                 Williams
                                                         Gra mercy
                                                         Colonial Sugar
                                                         Kaiser
                                                         LaRoche
                                                         CM Caceon
                                                                    Shell (Metairie)
                                                                     Air Products
                                                                     BOC Gases
                                                                     Folger
               Below Sunshine
               IMC-Agrico
               Chevron
                                                 Across River
                                                 (From NewOrlean
                                                 Witco
                                                 Monsanto
                                                 Cytec (Am CyarYamid)

                                    Norco
                                    Motiva (Shell NMC)
                                    Shell Chemical
                                    Air Liquide
                                    Orion (TransAmerican)
                                    CM Carbon
                                    Union Carbide
    Plaquemine
    Georgia Gulf
    Ashland
    Air Liquid
    Praxair
Donaldsonville
CF
Borden (Melamine)
Triad #1
Triad #2 (Ampro)
                                     Domino Sugar
                                     CM Carbon
                                     Chalmette Ref (Mobil)
                                     Murphy
                                     Am ax
                                     IMC-Agrico
                                     OxyChem (Hooker)
                                     Montell
                                     Witco
                                     Praxair
                                     Union Carbide
                                         Belle Chasse
                                         Chevron
                                                                                     son, R.W., 2000
                                                                           BP Amoco

-------
       Expanded Agricultural Chemical Complex
clay-
settling
ponds
reclaim
old mines
phosphate
rock
[Ca3(PO4)2...]
mine

Frasch
mines/
wells

Claus
recovery
from HC's


1 .2262
IP
air
decant water
fines
(clay, P2O5)
tailings
(sand)
rock slurry
slurry water
sulfur 1.2262



natural gas

air 7.8474
BFW 5.8947
H2O 0.7366
0.5880
bene-
-fici- >75 BPL
-ation <68 BPL
plant

sulfuric
acid
plant
3.7587
6.0392
1 .9529
0.4245
2.9293
0.0123
^ HP steam


fuel 0.0501
BFW 1 .2032

air 0.7088
0.2702
steam
0.5143

power
gene-
-ration


ammonia
plant

3.8751
0.8454
0.1374
1.8115
TJ
NH3
CO2
H2O
purge


7.8388
rock 4.6568
rain 100'sof
decant acres of
water Gypsum
Stack



H2SO4 3.7587
vent
LP steam
blowdown
others
LP
H2O
CO2
elctricity
0.6478
0.7412
0.0923
0.0120

other use
2.9102
0.6320

emission
2.8804
H2O
0.5372




evaporated
gypsum


slurried gypsum
5.7784
phosphoric
acid
plant
H2SIF6 0.0260
H2O
SiF4 1.8504
rock vapor
0.0305
0.3310 Granular
H2O Triple
2.9061 P2O5 0.5522 Super
cooled
LP 2.8804
H2O 4.2336
others 1 .9970

Phosphate
H3PO4 selling 0.0290
H2O
0.1285 |
P2O5 2.3249 Mono-

0.9231

0.7
air
0.0484
NH3

0.0567
CO2 0.0732
LP steam
0.0374
CO2 0.0315
H2O 0.0255
0.0341





NH3 0.4944 & Di-
0.0281 Ammonium
417
vent
nitric
acid plant


urea
plant


methanol
plant


0.1008 H2O for DAP %N
control
0.0000 NH3
|
HNO3 0.3306 0.2184

urea
Phosphates
urea granulation



0.3306 Ammonium NH4NO3 0.0278
NH3 Nitrate plant H2O
0.0483 0.0319
0.0281
UAN
urea plant
0.0326
urea 0.0717
H2O 0.0299
cw 0.0374
NH3 0.0001
CO2 0.0001
CO2 0.0045
vent
0.0044
0.0004
CH3OH 0.0863

acetic
acid acetic acid
(standard) H2O

0.0907
CH4 0.0005
Plants in the lower Mississippi River Corridor, Base Case. Flow Rates in Million Tons Per Year

-------
Some Chemical Complexes in the World
Continent
North America
South America
Europe
Asia
Oceania
Africa
Name and Site
•Gulf coast petrochemical complex in Houston area (U.S.A.)
and
•Chemical complex in the Baton Rouge-New Orleans Mississippi River Corridor (U.S.A.)
•Petrochemical district of Camacari-Bahia (Brazil)
•Petrochemical complex in Bahia Blanca (Argentina)
•Antwerp port area (Belgium)
•BASF in Ludwigshafen (Germany)
•The Singapore petrochemical complex in Jurong Island (Singapore)
•Petrochemical complex of Daqing Oilfield Company Limited (China)
•SINOPEC Shanghai Petrochemical Co. Ltd. (China)
•Joint- venture of SINOPEC and BP in Shanghai under construction (2005) (China)
•Jamnagar refinery and petrochemical complex (India)
•Sabic company based in Jubail Industrial City (Saudi Arabia)
•Petrochemical complex in Yanbu (Saudi Arabia)
•Equate (Kuwait)
•Petrochemical complex at Altona (Australia)
•Petrochemical complex at Botany (Australia)
petrochemical industries complex at Ras El Anouf (Libya)
Notes
•Largest petrochemical complex in the world, supplying
nearly two-thirds of the nation's petrochemical needs
•Largest petrochemical complex in the southern
hemisphere
•Largest petrochemical complex in Europe and world
wide second only to Houston, Texas
•Europe's largest chemical factory complex
•World's third largest oil refinery center
•Largest petrochemical complex in Asia
•World's largest polyethylene manufacturing site
•World's largest & most modern for producing ethylene
glycol and polyethylene

one of the largest oil complexes in Africa

-------
   COo Emissions from Industries
CO IUU
o 90 J

.2 ^ 80
-b c
CD CD 70
E 75
c > 60
1 t 50-
£ g 40
c -E 30
O O3
'co ° 20
CO
E 10
n 4
U n






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3 £
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All other
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5
Total Energy-Related Carbon Dioxide Emissions for
     Selected Manufacturing Industries, 1998,
              from EIA, 2001

-------
  Carbon Dioxide Emissions  and Utilization
              (Million Metric Tons Carbon Equivalent Per Year)
 C02 emissions and utilization
               Reference
Total C02 added to atmosphere
      Burning fossil fuels
      Deforestation
                                                IPCC(1995)
 5,500
 1,600
Total worldwide C02 from consumption and flaring of fossil
                                                EIA (2002)
fuels
      United States
      China
      Russia
      Japan
      All others
 1,526
  792
  440
  307
3,258
 U.S. C02 emissions
      Industry
      Buildings
      Transportation
      Total
                                                Stringer (2001)
  630
  524
  473
1,627
 U.S. industry (manufacturing)
	Petroleum, coal products and chemicals   175
                                                EIA (2001)
 Chemical and refinery (BP)
      Combustion and flaring                97%
      Noncombustion direct C02 emission      3%
                                                McMahon(1999)
Agricultural chemical complex in the lower Mississippi River
corridor excess high purity C02	0.183
                                                Hertwig et al. (2002)
 C02 used in chemical synthesis
      30
                                                Arakawaetal. (2001)

-------
       Commercial Uses of CO
110 million tons of CO2 for chemical synthesis
- Urea (chiefly, 90 million ton of CO2)
- Methanol (1.7 million tons of CO2)
- Polycarbonates
- Cyclic carbonates
- Salicylic acid
- Metal carbonates

-------
          Surplus Carbon Dioxide

Ammonia plants produce 1.2 million tons per
year in lower Mississippi River corridor

Methanol and urea plants consume 0.15
million tons per year

Surplus high-purity carbon dioxide 1.0 million
tons per year vented to atmosphere

-------
             Greenhouse Gases as Raw Material
          ef fin* chsmkali
thi chsmlcal
-CiOjO-. Acids, asltrs, laclonw
          Cirtwnlo
-N€O:
USB am u aulvant
Energy lidi praducia
CO,
From Creutz and Fujita, 2000
                                           ox
RWICOflfif
                                CHfH

-------
 Catalytic Reactions  of CO2 from Various Sources
Hydrogenation                               Hydrolysis and Photocatalytic Reduction
                         methanol          CO0 + 2H0O^ ChLOH + O0
CO2 + 3H2 -» CH3OH + H2O
2CO2 + 6H2 -» C2H5OH + 3H2O  ethanol
CO2 + H2
          CH-O-CH
                         dimethyl ether
CO2 + H2O -» HC=O-OH + 1/2O
CO2 + 2H2O -» CH4 + 2O2
Hydrocarbon Synthesis
CO2 + 4H2 -» CH4 + 2H2O
           C2H4 + 4H2O
                         methane and higher HC
                         ethylene and higher olefins
Carboxylic Acid Synthesis
          HC=O-OH
CO2 + H2 -
CO2 + CH4
           CH-C=O-OH
Graphite Synthesis
CO2 + H2 -» C + H2O
Amine Synthesis
CO2 + 3H2 + NH3-
                         formic acid
                         acetic acid
Other Reactions
CO2 + ethylbenzene ->styrene
CO2 + C3H8 -» C3H6 + H2 + CO
         dehydrogenation of propane
CO2 + CH4 -» 2CO + H2  reforming
                            ^ C + H2
                         CO2 + 4H2 -» CH4 + 2H2O
               CH3-NH2 + 2H2O
                                  methyl amine and
                                  higher amines

-------
Application of the System to Chemical Complex in
      the Lower Mississippi River Corridor
     • Base case
       Superstructure
       Optimal structure

-------
                 Base Case of Actual Plants
clay-
settling
ponds
reclaim
old mines
phosphate
rock
[Ca3(PO4)2...]
mine

Frasch
mines/
wells

Claus
recovery
from HC's


1 .2262
IP
air
decant water
fines
(clay, P2O5)
tailings
(sand)
rock slurry
slurry water
sulfur 1.2262



natural gas

air 7.8474
BFW 5.8947
H2O 0.7366
0.5880
bene-
-fici- >75 BPL
-ation <68 BPL
plant

sulfuric
acid
plant
3.7587
6.0392
1 .9529
0.4245
2.9293
0.0123
^ HP steam


fuel 0.0501
BFW 1 .2032

air 0.7088
0.2702
steam
0.5143

power
gene-
-ration


ammonia
plant

3.8751
0.8454
0.1374
1.8115
TJ
NH3
CO2
H2O
purge


7.8388
rock 4.6568
rain 100'sof
decant acres of
water Gypsum
Stack



H2SO4 3.7587
vent
LP steam
blowdown
others
LP
H2O
CO2
elctricity
0.6478
0.7412
0.0923
0.0120

other use
2.9102
0.6320

emission
2.8804
H2O
0.5372




evaporated
gypsum


slurried gypsum
5.7784
phosphoric
acid
plant
H2SIF6 0.0260
H2O
SiF4 1.8504
rock vapor
0.0305
0.3310 Granular
H2O Triple
2.9061 P2O5 0.5522 Super
cooled
LP 2.8804
H2O 4.2336
others 1 .9970

Phosphate
H3PO4 selling 0.0290
H2O
0.1285 |
P2O5 2.3249 Mono-

0.9231

0.7
air
0.0484
NH3

0.0567
CO2 0.0732
LP steam
0.0374
CO2 0.0315
H2O 0.0255
0.0341





NH3 0.4944 & Di-
0.0281 Ammonium
417
vent
nitric
acid plant


urea
plant


methanol
plant


0.1008 H2O for DAP %N
control
0.0000 NH3
|
HNO3 0.3306 0.2184

urea
Phosphates
urea granulation



0.3306 Ammonium NH4NO3 0.0278
NH3 Nitrate plant H2O
0.0483 0.0319
0.0281
UAN
urea plant
0.0326
urea 0.0717
H2O 0.0299
cw 0.0374
NH3 0.0001
CO2 0.0001
CO2 0.0045
vent
0.0044
0.0004
CH3OH 0.0863

acetic
acid acetic acid
(standard) H2O

0.0907
CH4 0.0005
Plants in the lower Mississippi River Corridor, Base Case. Flow Rates in Million Tons Per Year

-------
          Processes in the Superstructure
Processes in Superstructure
Processes in Base Case
Ammonia
Nitric acid
Ammonium nitrate
Urea
UAN
Methanol
Granular triple super phosphate
MAP & DAP
Power generation
Contact process for Sulfuric acid
Wet process for phosphoric acid
Acetic acid-conventional process
Electric furnace process for phosphoric acid
HCI process for phosphoric acid
Ammonium sulfate
SO2 recovery from gypsum process
S & SO2 recovery from gypsum process
Acetic acid - new CO2-CH4 catalytic
process

-------
Superstructure

-------
            Superstructure Characteristics

Options

- Three options for producing phosphoric acid
- Two options for producing acetic acid
- One option for sulfuric acid
- Two options for recover sulfur and sulfur dioxide
- New plants for
      ammonium sulfate
      recover sulfur and sulfur dioxide

Mixed Integer Nonlinear Program
594  continuous variables
  7  integer variables
505   equality constraint equations
      for material and energy balances
 27   inequality constraints for availability of raw materials
      demand for product, capacities of the plants in the complex

-------
                Raw Material and Product Prices
Raw Materials
Natural Gas
Phosphate Rock
     wet process
     electrofurnace
     HCI process
     GTSP process
HCI
Sulfur
     Frasch
     Glaus
C electrofurnace
Cost ($/mt)
     245
Raw Materials
Cost ($/mt)  Products
     27
     24
     25
     30
     50

     42
     38
     760
Market cost for short term
purchase
Reducing gas           1394
Wood gas              634
Sustainable Costs and Credits
Credit for CO2
Consumption
Debit for CO2
Production
Credit for HP Steam
Credit for IP Steam

Credit for gypsum
Consumption
Debit for gypsum
Production
Debit for NOX
Production
     6.50

     3.25

     10
     6.4

     5

     2.5

     1025
Ammonia
Methanol
Acetic Acid
GTSP
MAP
DAP
NH4NO3
UAN
Urea
H3P04
(NH4)2SO4
Price ($/mt)
190
96
623
142
180
165
153
112
154
320
187

-------
clay- decant water
settling fines
ponds (c ay, P205)
reclaim tailings
old mines
(sand)
phosphate
rock rock slurry
[Ca3(PO4)2...] _ surrywater
mine

Frasch
mines/
wells

Claus 0.9315
recovery
from HC's \
IP
air
natural gas

sulfur 0.9315
air 5.9621
BFW 4.4785
H2O 0.5596
0.4467


rain 100'sof
decant acres of
water Gypsum
Stack
bene-
-fici- >75 BPL
-ation <68 BPL
plant

2.8556
4.5883
sulfuric 1.4837
acid 0.3226
plant 2.2255
0.0093
^ HP steam


fuel 0.0231
BFW 0.5552

air 0.7200
0.2744
steam
0.5224

2.6276
power 0.5998
gene- 0.0634
-ration 1.1954
TJ


NH3
CO2
ammonia
plant H2O
purge







3.9194
rock 2.3284
H2SO4 1 .8794
vent I
LP steam I
blowdown |
others ]
I
LP !
H2O ]
CO2 |
elctricity j
i
0.6581 '
0.7529 I
I
0.0938 ]
0.0120 !
I
other use i
2.6524 I
|
i
0.6788 I
emission i
I
I
I
i
i
1 .4402
H2O
0.2686
O.C
0.4615 air
0.0242
NH3



evaporated \J \J LI 1 1 1 Cl 1 V.
1
gypsum

JU UlslUI C
slurried gypsum
2.8892
phosphoric
acid
plant


708
vent
nitric
acid plant

0.0283
CO2 0.0366
LP steam
0.0187
CO2 0.0315
H2O 0.0255
0.0341
1
0.0060
0.0022
i
i
[H2SO4 0.9763

NH3 0.3341


urea
plant

methanol
plant

acetic
acid plant

ammonium
sulfate plant

H2SIF6 0.0130
H2O
SiF4 0.9252
H2O
1 .4531 P2O5
cooled
LP 1 .4402
H2O 2.1168
others 0.9985
F
t

0.0504 H2O for DAP c
con
0.0000 NH3
|
HNO3 0.1653 0.1050

urea
urea
H2O
cw
NH3
CO2
vent
0.1653 Ammonium NH
NH3 Nitrate plant H2O
0.0241 0.0061
0.0140
0.0359
0.0150
0.0187
0.0000
0.0000
0.0004
rock vapor
0.015
0.1655 Granular
Triple
0.2761 Super
Phosphati
H3PO4 selling 0.0145
H2O
0.0642 |
32O5 1.1625 Mono-
•JH3 0.2473 & Di-
0.0140 Ammoniur
/oN Phosphate
rol urea granulatio



4NO3 0.0279
UAN
urea plant
0.0326


CH3OH

0.0907
0.0082

acetic acid

1 .2958

ammonium sulfate
H2O 0.0146


-------
Comparison of Base Case and Optimal Structure

Profit (U.S.$/year)
Environmental cost (U.S.$/year)
Sustainability cost (U.S.$/year)
Plant name

Ammonia
Nitric acid
Ammonium nitrate
Urea
Methanol
UAN
MAP
DAP
GTSP
Contact process sulfuric acid
Wet process phosphoric acid
Electric furnace phosphoric acid
HCI to phosphoric acid
Ammonium sulfate
Acetic acid (standard)
Acetic acid (new)
S02 recovery from gypsum
S & S02 recovery from gypsum
Ammonia sale
Ammnium Nitrate sale
Urea sale
Wet process phosphoric acid sale
Methanol sale
Total energy requirement from fuel gas





Capacity (mt/year)
(upper-lower bounds)
329,030-658,061
0-178,547
113,398-226,796
49,895-99,790
90,718-181,437
30,240-60,480
0-321,920
0-2,062,100
0-822,300
1,851,186-3,702,372
697,489-1,394,978
697,489-1,394,978
697,489-1,394,978
0-2,839,000
0-8,165
0-8,165
0-1,804,417
0-903,053







Base case
148,087,243
179,481,000
-17,780,800
Capacity
(mt/year)
647,834
178,525
226,796
99,790
90,719
60,480
321,912
2,062,100
822,284
3,702,297
1,394,950
na
na
na
8,165
na
na
na
0
218,441
39,076
13,950
86,361





energy
requirement
(TJ/year)
3,774
-649
116
127
1,083
0

2,127
1,036
-14,963
7,404
na
na
na
268
na
na
na





2,912

Optimal structure
246,927,825
123,352,900
-16,148,900
Capacity
(mt/year)
658,061
89,262
113,398
49,895
90,719
60,480
160,959
1,031,071
411,150
2,812,817
697,489
0
0
1,295,770
0
8,165
0
0
0
105,043
3,223
6,975
90,719





energy
requirement
(TJ/year)
3,834
-324
26
63
1,083
0

1,063
518
-11,368
3,702
0
0
726
0
92
0
0





1,344


-------
           Comparison of Acetic Acid Processes
Process
Conventional Process
New Catalytic Process
Raw Materials
Methanol,
Carbon Monoxide
Methane,
Carbon Dioxide
Reaction Condition
450K, SObar
350K, 25bar
Conversion of
methane
100%
97%
Equipment
reactor,
flash drum,
four distillation columns
reactor,
distillation column

-------
             Production Costs for Acetic Acid
                           Moulijn, etal., 2001
Plant Production Cost,
(cents per kg)
   Methanol
Carbon Monoxide
   Methane
Carbon Dioxide
Raw materials
     21.6
    21.6
Utilities
      3.3
     1.7
Labor
      1.2
     1.2
Other (capital, catalyst)
      10.1
     10.1
Total Production Cost
     36.2
    34.6
Current market price 79 cents per kg

-------
         Catalytic Process for Acetic Acid
Capacity:  100 million pound per year of acetic acid
         36,700 tons per year of carbon dioxide raw material
Potential Savings
Reduction in utilities costs for process steam $750,000
Energy savings from not having to produce this steam
      275 trillion BTUs per year
Reduction in NOx emissions base on steam and power generation
      by cogeneration
      3.5 tons per year
Reduction in carbon dioxide emissions
      12,600 tons per year from the steam production
      36,700 tons per year conversion to a useful product

-------
Develop Process Information for the System

  •  Simulate process using HYSYS and Advanced
       Process Analysis System.

  •  Estimate utilities required.

  •  Perform economic analysis.

  •  Obtain process constraint equations from HYSIS and
    Advanced Process Analysis System.

  •  Maximize the profit function to find the optimum
    process configuration with the System.

  •  Incorporate into superstructure.

-------
HYSYS Process Flow  Diagram for Acetic Acid Process
             reeyde-GLH
                          RCY-1
                Recyc
from
pipeline
                  MIX-100
                         Mixer
                         Out
           Feed
                            Hea!m  =
                                      Vapor ^)G?   HAc-COl
                                      Product  £-100  Mixture
                                   CRtf-100
                  X
Liquid   f —
Product  E-101
           Cou rig
           H2O
                     X-100
                                                              *-
                                                     Liquid
                                                     Product
                                                         A':"^I'Vy/   Acutic

                                                           MIX-102  Product

-------
    Advanced Process Analysis System
                Advanced Process
                 Analysis System
              On-Line Optimization
Process Control
Process Modification
 Flowsheet]
 Simulatioi
Reactor
Analysis
Pinch
Analysis
Pollution
Assesment
^	J
  Fig.  1 Overview of Advanced Process Analysis System

-------
       On-Lirie Optimization
 setpoints
   for
controllers
                                plant
                            measurements
              Distributed Control System
  optimal
  operating
  conditions
                                        sampled
                                        plant data
setpoint
targets
   Gross Error
    Detection
      and
Data Reconcilation
 Optimization Algorithm
    Economic Model
      Plant Model
          updated plant
          parameters
                                         reconciled
                                         plant data
     Parameter
     Estimation
     economic model
       parameters

-------
                   Reactor Analysis
                           Reactor Type
        Homogeneous
                                              Heterogeneous
  y
Gas Phase
         Liquid Phase
 PFR,
 CSTR,
 Batch
Reactors
1
G

y
Catalytic
r y y
as Liquid Gas-Liq
^^ ^^rf

y
Gas-Liquid
1
uid CSTR
Bubble
Reactor
Packed Bed
                                 Fixed Bed
                                  And
                                  Fluidised Bed
                                  Reactors
  Trickle Bed
Fixed Bubble Bed
  CSTR Slurry
  Bubble Slurry
   3-Phase
Fluidised Bed

-------
Energy Integration - Pinch Analysis
     0  100  200 300  400 500
           Q(W)
100 200  300 400  500
   Q(W)
      H2
       KlM>=d
       KD	
        ( ) Heater  \ ) Cooler \ ) Heat Exchanger  Loop

-------
                Pollution Assessment
           Waste Reduction Algorithm (WAR) and
                Environmental Impact Theory
Pollution Index
I = wastes/products = - (SOut + ^Fugitive) / SPn
Potential Environmental Impact
 a,   relative weighting factor
    } units of potential environmental impact/mass of chemical k

-------
                Conclusions

The System has been applied to an extended
agricultural chemical complex in the lower Mississippi
River corridor
Economic model incorporated economic, environmental
and sustainable costs.
An optimum configuration of plants was determined with
increased profit and reduced energy and emissions


For acetic acid production, new catalytic process is
better than conventional process based on energy
savings and the reduction of NOX and CO2 emissions.

-------
             Conclusions

Based on these results, the methodology
could be applied to other chemical complexes
in the world for reduced emissions and
energy savings.

The System includes the program with users
manuals and tutorials. These can be
downloaded at no cost from the LSU Mineral
Processing Research Institute's web site
www.mpri.lsu.edu

-------
             Future Work
Add new processes for carbon dioxide

Expand to a petrochemical complex in the
lower Mississippi River corridor
Add processes that produce fullerines and
carbon nanotubes

-------
  Advanced Process Analysis System
On-Line Optimization and Flowsheet Simulation
      accurate description of the plant
      maintain optimum operating conditions

Pinch Analysis
      minimum utilities, steam and cooling water

Chemical Reactor Analysis
      select best chemical reactor from options

Pollution Assessment - WAR Algorithm
      identify sources of pollutant generation
      in the plant and process modifications

-------
    Advanced Process Analysis System
                Advanced Process
                 Analysis System
              On-Line Optimization
Process Control
Process Modification
 Flowsheet]
 Simulatioi
Reactor
Analysis
Pinch
Analysis
Pollution
Assesment
^	J
  Fig.  1 Overview of Advanced Process Analysis System

-------
 Advanced Process Analysis  System Structure
Process
Specification :
 PFD, units, streams,
 physical properties
Key word index:
Unit ID, Stream ID,
Component ID,
Property ID
DataBase of APAS:

PFD:  units & streams
Unit:  local variables
      parameters
      balance equations
      stream connection
Streams: global variables
Plant data
Property: enthalpy function
        density, viscosity
FS:   simulation data
OLO:  optimal setpoints
      reconciled data
      estimated parameters
RA:   reactor comparison
      best reactor for the
      process
PA:   best heat exchanger
      network
PI:    pollution information
                                               Units, streams,
                                               physical property
 Simulation data


  Units, streams,
  physical property
  plant data	
  Optimal setpoints,
  reconciled data,
  parameters

  Temp., flow rates
  enthalpy function .
Flowsheet
Simulation
:On-Line
Optimization
                                               Reactor comparison

                                               Temp., flow rates
                                               enthalpy function
  Best heat exchanger
  network
  Reactor
  Analysis


  Pinch
  Analysis
Flow rates, composition [ Pollution
                                               "Pollution information  I Index
   Fig.  2 Database Structure of Advanced Process Analysis System

-------
            On-Line Optimization

Automatically adjust operating conditions
with the plant's distributed control system

Maintains operations at optimal set points

Requires the solution of three NLP's
      gross error detection and data reconciliation
      parameter estimation
      economic optimization

            BENEFITS

Improves plant profit by 3-5%
Waste generation and energy use are reduced
Increased understanding of plant operations

-------
       On-Lirie Optimization
 setpoints
   for
controllers
                                plant
                            measurements
              Distributed Control System
  optimal
  operating
  conditions
                                        sampled
                                        plant data
setpoint
targets
   Gross Error
    Detection
      and
Data Reconcilation
 Optimization Algorithm
    Economic Model
      Plant Model
          updated plant
          parameters
                                         reconciled
                                         plant data
     Parameter
     Estimation
     economic model
       parameters

-------
Some Companies Using On-Line Optimization
                    Eur
                    OMV Deutschland
                    D ow Benelux
                    Shell
                    OEMV
                    Penex
                    Borealis AB
                    DSM -Hydrocarbons
U nited States
Texaco
Amoco
Conoco
Lyondel
Sunoco
Phillips
M arathon
Dow
C hevron
Pyrotec/KTI
NOVA Chemicals (Canada)
British Petroleum

Applications
mainly crude units in refineries and
ethylene plants

-------
Companies Providing On-Line Optimization


    Aspen Technology - Aspen Plus On-Line
         -  DMC Corporation
         -  Setpoint
         -  Hyprotech Ltd.

    Simulation Science - ROM
         -  Shell - Romeo

    Profimatics - On-Opt
         -  Honeywell

    Litwin Process Automation - FACS

    DOT Products, Inc. - NOVA

-------
On-Line Optimization Problem Size
      Contact    Alkylation    Ethylene
Units
Streams
Constraints
Equality
Inequality
Variables
Measured
14
35

761
28

43
Unmeasured 732
Parameters
11
76
110

1579
50

125
1509
64
                              -4,000
                             -400,000
                              -10,000
                               -300
                             -10,000
                               -100

-------
   Key Elements

 Gross Error Detection

 Data Reconciliation

 Parameter Estimation

 Economic Model
 (Profit Function)

 Plant Model
 (Process Simulation)

Optimization Algorithm

-------
Status of Industrial Practice for On-Line Optimization
     Steady state detection by time series screening



     Gross error detection by time series screening




     Data reconciliation by least squares




     Parameter estimation by least squares




     Economic optimization by standard methods

-------
Plant data
from DCS
 ombined gross
;rror detection and
lata reconciliation
                                               Plant model
Simultaneous data
reconciliation and
parameter estimation
                                                   I
                                               Optimization
                                               algorithm
Plant
economic
optimization
   Optimal
•^setpoints
   to DCS

-------
         Data Reconciliation
Adjust process data to satisfy m ate rial

and energy balances.

Measu re ment error- e

      e = y - x

y = measured process variables
x = true values of the measured
variables
        = y + a
a - m easurem ent adjustm ent

-------
                Data Reconciliation NLP
Measurements having only random errors - least squares
                                 2
                       n
             Minimize:^
                x     1=1 v
             Subject to:  f(x) = 0
           ai - standard deviation of y




            f(x) - process model


                - linear or nonlinear

-------
        Types of Gross Errors
             Types of Gross Errors
       ooo Correct Dala
Corrupted Data
    (a) Bias
    00°
               time
                            I
                            T
                         0 °

                                          time
(b) Complete Failure
                           1
                           1
                           1

                           *
            ijme
   (c) Drifting
(d) Precision Degradation
Source: S. Narasimhanand C. Jordache, Date Reconciliation and Gross
Error Detection, Gulf Publishing Company, Houston, TX (2000)

-------
  Gross Error Detection Methods
Statistical Testing
o many methods
o can include data reconciliation
Others
 o principal component analysis
 o ad hoc procedures - time series screening

-------
   Combined Gross Error Detection and Data
                   Reconciliation

Measurement Test Method - least squares
         Minimize:     (y - x)TQ-1(y - x) = eTQ-1e
             x, z
         Subject to:    f(x, z, 6)=0
                          XL < X < XU
                          ZL < Z < ZU
Test statistic:
   if 6j |/Oj > C measurement contains a gross error

Least squares is based on only random errors being present
Gross errors cause numerical difficulties
Need methods that are not sensitive to gross errors

-------
    Methods Insensitive to Gross Errors
Tjao-Biegler's Contaminated Gaussian Distribution
                                       x,,G)
P(Yj  Xj, R) = probability distribution function for the
random error
P(Yj  Xj, G) = probability distribution function for the
gross error.

-------
 Results of Theoretical and Numerical Evaluation
Method based on contaminated Gaussian distribution
had best performance for measurement containing
random errors and gross errors in the range 3o - 30o.

Method based on Lorentzian distribution had best
performance for measurement containing  random errors
and gross errors larger than 30o.

Measurement test method had the best performance
when only random errors were present. Significant
error smearing (biased estimation) occurred for gross
errors greater than 10o.

-------
       Parameter Estimation

     Error-in-Variables Method


Least squares


      Minimize',  (y - x)TQ~1(y - x) = eTQ~1e
         9
      Subject to:     f(x, 6) = 0

                    0 - plant param eters


Simultaneous data reconciliation and
param eter estim ation


      Minimize',  (y - x)TQ'1(y - x) = eTI~1e
         x,6
      Subject to:     f(x, 6) = 0


another nonlinear programm ing problem

-------
Three Similar Optimization Problems

     Three Similar Optimization Problems

     Optimize:     Objective function
     Subject to:    Constraints are the plant
                  model

     Objective function

        data reconciliation - distribution function
        parameter estimation - least squares
        economic optimization - profit function

     Constraint equations

        material and energy balances
        chemical reaction rate equations
        thermodynamic equilibrium relations
        capacities of process units
        demand for product
        availability of raw materials

-------
     Interactive On-Line Optimization Program

1.   Conduct combined gross error detection and data
    reconciliation to detect and rectify gross errors in plant
    data sampled from distributed control system using the
    Tjoa-Biegler's method (the contaminated Gaussian
    distribution) or robust method (Lorentzian distribution).

This step generates a set of measurements containing
only random errors for parameterestimation.

2.   Use this set of measurements for simultaneous
    parameter estimation and data reconciliation using the
    least squares method.

This step provides the updated parameters in the plant
model for economic optimization.

3.   Generate optimal set points for the distributed control
    system from the economic optimization using the updated
    plant and  economic models.

-------
Interactive On-Line Optimization  Program

    Process and economic models are entered as
    equations in a form similar to Fortran

    The program writes and runs three GAMS
    programs.

    Results are presented in a summary form, on a
    process flowsheet and in the full GAMS output

    The program and users manual (120 pages) can
    be downloaded from the LSU Minerals
    Processing Research Institute web site

       URLhttp:/A/vww. mpri. lsu.edu

-------
Opening Screen of On-Line Optimization Program
     JJJ Instructions
        setpoints for
        controllers
                    Plant
                    measurements
                  Distributed Control System
        optimal
        operating
        conditions
setpoint
targets
                                       Sampled
                                       plant data
  Gross Error
 Detection and
Data Reconcilation
       E con om ic 0 ptim izatio n
          Economic Model
           Plant Model
       updated plant
       param eters
                                       Reconciled
                                       plant data
    Parameter
    Estimation
            economic
            param eters
   On-line optimization adjusts the
 operation of a plant to maximize the
profits and minimize the emissions by
providing the optimal setpoints of the
  Distributed Control System (DCS).


   Create New Model.  Requires:

   a. Plant Model

   b. Economic Model

   c. Parameters

   d. DCS Data

(* iQjpen Enisling Model;

   Revise Plant Information
                                                       OK
                                               Cancel
                                            Help
                                 f" ]Do not display this window next time

-------
Algorithm Selection in On-Line optimization  Program
   III Interactive On line Optimization - E:\OFFICE\PRWIN\FILESUoQ\EKamplesUefineiy.ioo
   File  View  Help
     kl ode I Description   |    Tables   |    Measured Variables   |   Unmeasured Variables   |    Plant Parameters
      Equality Constraints    I    Inequality Constraints        Optimization Algorithms        Constant Properties
                Data Validation Algorithm:

                P ar am e te rs E stirri at i on A Igo rithrn;
 Tioa-Gieqler Method [moderate qross errors
I Least Squares Method [snail qross errors!
 Tioa-Bieqler Method [moderate qross errors]
                                         Robust Function [large qross errors]
                Economic Optimisation Objective Function:
                -33'crude+O.OI 9651gad-2.5ysrnrf+0.019651grf-2.2xsrdscc-2.2:<3r[occ+Ci.019G5>:fgcc+ *
                Optimization Direction:

                Economic Model Type:
 Maximizing
 Linear

-------
Steady
State
Detection for
On-Line
Optimization
              Distributed Control System
Selected plant    X
measurements^—-^-
                  PIant Steady?
                                  No
Plant Model: 	L^
Measurements  :
Equality constraints
                      I
          Data Validation
              l
                                                                      No:
                                                    Successful solution
                                  Plant Model:    >
                                  Equality constraints
                                                         I
                         Validated measurements
                 Parameter Estimation
                                                    Successful solution
                                                                         No
                                                          I  Updated parameters
                                   Plant model 	
                                   Economic model
                                   Controller limits
                                   Selected plant
                                   measurements &
                                   controller limits
                Economic Optimization
                                                                        No
                                                     Plant Steady?
                      7
                                                    Optimal Setpoints

-------
  Some Other Considerations
Redundancy

Observeability

Variance estimation

Closing the loop

Dynamic data reconciliation
 and parameter estimation

-------
         On-Line Optimization Summary
                     Summary

Most difficult part of on-line optimization is developing and
validating the process and economic models.

Most valuable information obtained from on-line
optimization is a more thorough understanding of the
process

-------
Process Flow Diagram for Contact Process
          Sulfur

          Burner
                                Acid Towers
                                Pump Tank
                                98% H2SO4
                                                 f 93% H2SO4
                                                   product
Acid Dilution Tank
 93% H2SO4

-------
         Validation of Contact Process  Model
Table 4-14 The Comparison of Model Prediction and Plant Design Data
for Converter I
                                      Design Data          Model Prediction
        FSO2 (In-0ut), Kmol/sec            0.337 - 0.129            0.337 - 0.129
        FSOs (In-0ut), Kmol/sec            0.007 - 0.215            0.007 - 0.215
        FO2 (Mt\ Kmol/sec             0.280 - 0.176            0.280 - 0.176
        FN2 0*-°°*, Kmol/sec             2.373 - 2.373            2.373 - 2.373
        Conversion of SO2                 62.5%                62.5%
        Temp. (S06 - S07), K            693.2 - 890.2            692.5 - 890.9
        Effectiveness factor                  -                   0.241

-------
Contact Process Economic Optimization
     Economic Optimization
 Value Added Profit Function
  On-Line Optimization Results

                   Profit
          Current    Optimal
  Date     ($/day)    ($/day)      Improvement

  6-10-97    37,290    38,146       2.3%
                               $313,000/yr

  6-12-97    36,988    38,111       3.1%
                              $410,000/yr

-------
  Contact Process Potential Improvement
On-Line Optimization



Increased profit by 3%($350,000/yr)



Reduction in sulfur dioxide emissions by 10%



Improved understanding of the process

-------
                       Alkylation
Isoparaffin-olefin alkylation produces branched paraffins in the
      gasoline range
Refineries use C3C4 and C5 hydrocarbon streams
Sulfuric acid catalyst concentration maintained above 88% to
prevent polymerization
Reactor temperatures in the range of 10-20 °C
Alkylation is a two-phase system
      - low solubility of isobutane in the catalyst phase
      - intimate contact of the reactant and the catalyst
      - efficient mixing with fine subdivision

-------
              Motiva Alkylation Process
15,000 BPD STRATCO Effluent Refrigerated Alkylation Plant
STRATCO reactor contacts the reactants in a high velocity
propeller stream and removes heat from the exothermic reaction
Process flow diagrams
 prepared from P&ID's of the plant
 reaction section
 refrigeration, depropanizer and alkylate deisobutanizer sections
 saturate deisobutanizer section

-------
                        Reactor Section
Four reactors
and acid settlers
Three feed
streams
Olefin feed
(HC01)
 Isobutane feed
(HC03)
 Recycled
olefin/isobutane
(HC32)

-------
             Model Summary
Table 5.1. Summary of the Alkylation Process Model
Feature                      Quantity
Process Units                   76
Process Streams                110
Equality Constraints            1579
Inequality Constraints             50
Measured Variables             125
Unmeasured Variables          1509
Parameters                     64

-------
                                    Table 4.8. Plant vs. Model Data
    Model Validation

Establish accuracy of model to predict
performance of plant

Used data validation

125 measured plant variables, 88
were within the accuracy of the
measurements

Remaining 37 variables shown here
with standard measurement error
Process engineers concluded that
these 37 variables were within the
range of possible process values
Model  of  the   process  accurately
predicted its performance and can be
used for on-line optimization.
Variable Name
FAC02
FAC12
FAC23
FAC45
FC308
FC316
FC322
FC328
FC403
FC412
FSC411
FstmE612
X1C417
X2SC402
X2SC408
X3C325
X3SC403
X4C316
X4SC408
X5C316
X5C417
X5HC32
X6SC402
X6SC403
X7HC32
X7SC402
X7SC408
XX1C322
xx1C414
XX2HC01
xx3C407
XX3HC01
xx4C407
XX5C407
xx5C412
xx5C414
XX7C414
Plant Data
(yd
0.1125
0.1259
0.1253
0.1040
2.1990
0.6581
0.4427
0.0942
3.8766
0.0324
2.7287
0.1425
0.0372
0.0136
0.0221
0.0017
0.0103
0.0580
0.0331
0.0020
0.0009
0.0096
0.0167
0.0250
0.0197
0.0022
0.0022
0.0027
0.0330
0.4525
0.0003
0.3558
0.1124
0.0803
0.0022
0.0021
0.0015
Reconciled Data
from Data
Validation
(Xi)
0.1600
0.1600
0.1600
0.1600
3.1032
1.8000
1.5619
0.0535
2.2834
0.0418
1.3525
0.0889
0.0255
0.0084
0.0002
0.0000
0.0212
0.0796
0.0088
0.0060
0.0295
0.0306
0.0666
0.0950
0.0497
0.0032
0.0000
0.1167
0.0800
0.1291
0.0000
0.0125
0.0853
0.1506
0.0581
0.0011
0.0080
Standard
Measureme
nt Error
(6i)
4.2235
2.7085
2.7653
5.3846
4.1120
17.3515
25.2812
2.6399
4.1097
2.8968
5.0436
3.7607
3.1309
3.7929
9.9048
10.0000
10.5665
3.7155
7.3475
19.8000
286.2300
22.0134
29.8204
27.9946
15.2312
4.3956
10.0000
428.5338
14.2498
7.1481
7.4194
9.6498
2.4068
8.7555
255.6751
4.8325
44.4218

-------
  Alkylation Process Economic Model
Profit = Sales - Cost - Utilities
Sales = Alkylate (C3, C4 and C4 Raffinate)
          produced * Price of alkylate
Cost = X Input * Cost
Utilities = X Input * Utility Cost

-------
        Raw Material/Utility Costs and Product Prices
Table 5.4. Alkylation Plant Raw Material/Utility Costs and Product Prices
Feeds
Products
Product

Propylene
Butylene
Iso-butane
N-butane
C3 Alky late
C4 Alky late
C, Raffinate
Stream
Number
HC01
HC01
SC414
SC405, C413
C407
C407
C407
Cost and Price ($/bbl)
Summer
11.79
18.00
16.88
13.29
24.49
26.32
26.34

Winter
10.44
16.56
17.39
12.71
22.30
24.06
24.19
        Alky late
Catalyst and Utilities
        H2SO4(Stream AC02)
         Electricity
        50# Steam
         250# Steam
        600# Steam
Cost
$110/Ton
$0.04/KWH
$2.50/M-Lbs
$3.60/M-Lbs
$4.40/M-Lbs

-------
                   On-Line Optimization
Process Data from Distributed Control System
Plant measurement at 1.0 minute intervals over a two day period
Six steady state periods identified using time series with MathCAD graphics

Data Reconciliation and Gross Error Detection
Robust Lorentzian function method and CONOPT2
Optimal solution obtained in 1,200 iterations
Reconciled measurements reported and about 30 gross errors identified
Parameter Estimation and Data Reconciliation
Optimal solution obtained in 1,500 iterations
Small adjustments in values of parameters

-------
 On-Line Optimization Results Economic Optimization
Table 5.5. Calculated Profit  after Data Validation  (D.V.), Parameter Estimation (P.E.)  and
Economic Optimization (E.O.) Steps for six Different Operation Points (Steady States)
  Operation points  D.V.              P.E.             E.O      % Increase
        #1       11.9              12.1             29.1      144
        #2        7.4              7.4             21.4      189
        #3       21.4              22.1             26.9       26
        #4        7.0              7.0             22.1      216
        #5       10.1              23.3             26.3      160
        #6       22.0              23.6             27.6       25
                                      Average % increase    127
Improvement in profit
8.5% reduction in costs and 2.2% increase in sales
5.5% more olefin charge
98% reduction in isobutane purchase cost (because of reduced isobutane flow rate)
7.2% reduction in saturate feed to the Saturate Deisobutanizer column
2.2% increase in the alkylate (alkylate quality did not change at optimal operation)
Average of 9.4x109 BTU/yr in energy savings from steam usage in the distillation columns

-------
                   Reactor Analysis
                           Reactor Type
        Homogeneous
                                              Heterogeneous
  y
Gas Phase
         Liquid Phase
 PFR,
 CSTR,
 Batch
Reactors
1
G

y
Catalytic
r y y
as Liquid Gas-Liq
^^ ^^rf

y
Gas-Liquid
1
uid CSTR
Bubble
Reactor
Packed Bed
                                 Fixed Bed
                                  And
                                  Fluidised Bed
                                  Reactors
  Trickle Bed
Fixed Bubble Bed
  CSTR Slurry
  Bubble Slurry
   3-Phase
Fluidised Bed

-------
Contact Process Chemical Reactor Improvement
Chemical Reactor Analysis
Conversion could be increased by 19% in the first reactor.
Reactor volumes could be reduced by 87% by using a
reactor pressure of 10.3 atms rather than current operations
at 1.3 atms.

-------
Energy Integration -  Pinch Analysis
     0   100 200  300 400  500
           Q(W)
                       160
                       120
                     T(°C) 80
                       40
                        0
   C1+C2
0  100  200 300 400  500
      Q(W)
      H2
        KlM>=d
        KD	
        ( ) Heater \  ) Cooler   \ ) Heat Exchanger  Loop

-------
            Contact Process Pinch Analysis
  1400


  1200


_ 1000
^

2  800
 —
CD
   600
   400
   200
       0
500    1000   1500   2000   2500   3000   3500   4000

          Enthalpy (*10e5 KJ/Hr)
       Fig. 5 Grand Composite Curve for the Contact Process

-------
     Contact Process Pinch Analysis
Process is below the pinch, and no hot utilities
are required.
A proposed heat exchanger network has 25%
less area than the current one.

-------
          Energy Integration -  Pinch Analysis
    Alkylation process is very energy  intensive
    Alkylation process model has 28 heat exchangers, plus
    four contactors. Heat exchange in contactors not included
    in the pinch analysis
    Grand Composite Curve
    End points of the curve gives the minimum values of external heating and
    cooling required by the process
     480
     460
     440
     420
     400
Temperature 380
     280
             100
                   200
                          300
                                400     500
                                 Enthalpy (* 5)
                                             600
                                                   700
                                                         800
                                                                900

-------
Pinch Analysis - Maximum Energy Recovery Network
                        Diagram
   ;•" The Heat Exchanger Network Program - [The Network Grid Diagram]
    View Zoom Print Help Close
                                                      id-

-------
    Pinch Analysis - Minimum Utilities
Minimum Utilities
1742 MJ/min steam (external heat)
4043 MJ/min of cooling water (external cooling)
Current Operations
1907 MJ/min steam (external heat)
4300 MJ/min of cooling water (external cooling)

-------
   Pinch Analysis - Optimum Heat Exchanger
                  Configuration
Current Configuration
6 heat exchangers, 4 heaters and 12 coolers
Optimal Configuration
16 heat exchangers, 4 heaters and 15 coolers
Additional heat exchangers reduce energy requirements
May result in operational difficulties
See report for pressure shift applied to distillation columns

-------
             Pollution Assessment

    Assess the pollutants generated in the process
    Determine location of generation
    Modify process for waste minimization
     Contact Process Pollution Assessment

Process units identified for modification to reduce sulfur
dioxide emissions were the sulfur furnace and the four
packed bed reactors

-------
                Pollution Assessment
           Waste Reduction Algorithm (WAR) and
                Environmental Impact Theory
Pollution Index
I = wastes/products = - (SOut + ^Fugitive) / SPn
Potential Environmental Impact
 a,   relative weighting factor
    } units of potential environmental impact/mass of chemical k

-------
    Values used in Alkylation Process Model
Component
C3-
C4=
iC4
nC4
iC5
nC5
iC6
H2S04
Ecotoxicity
(aquatic)
0.0305
0.0412
0.1566
0.1890
0.0649
0.3422
0.2827
0.0170
Ecotoxicity
(terrestrial)
0
0.3012
0.2908
0.2908
0.2342
0.2342
0.1611
0.1640
Human
Toxicity
(air)
9.06E-7
0
8.58E-7
8.58E-7
0
5.53E-7
0
0.2950
Human
Toxicity
(water)
0
0.3012
0.2908
0.2908
0.2342
0.2342
0.1611
0.1640
Human
Toxicity
(soil)
0
0.3012
0.2908
0.2908
0.2342
0.2342
0.1611
0.1640
Photochemical
Oxidant
Formation
1.1764
1.6460
0.6473
0.8425
0.6082
0.8384
1.022
0
Source EPA National Laboratory for Sustainable Development

-------
                    Pollution  Assessment
Table 5.6. Input and Output Streams in Alkylation Process.

Stream   Description               Type            Pollution Index
AC02    Fresh Acid Feed           Input             0.808
HC01    OlefinFeed               Input             1.622
SC414   Make-up Isobutane         Input             1.611
SC401   Sat-Deisobutanizer Feed    Input             1.789
AC45    Spent Acid               Non-Product       1.034
C320    To LPG Storage           Product             0
C328    To Fuel Gas              Product             0
C407    To Alkylate Storage         Product             0
C413    To N-butane Storage       Product             0
SC405   To N-butane Storage       Product             0

-------
    Pollution Assessment before and after Economic

                             Optimization

Program calculates pollution indices for each input, produce and non-product stream
in the process

These values are used to calculate the six pollution indices for the process

Negative values mean that the input streams are actually more harmful to the
environment than the non-products if they are not processed through the alkylation
process

Table 5.7. Pollution Assessment Values (BEO) and after (AEO)

 Index Type                               Value
                                   (BEO)   (AEO)
Total rate of impact generation         -4.9120  -4.7966   impact/time
Specific impact generation           -3.2860 -3.4584  impact/product
Pollution generation per unit product    -0.9777  -0.9742  mass of pollutant/mass of product
Total rate of impact emission         1.0325  1.0337  impact/time
Specific impact emission             0.6897  0.7453  impact/product
Pollutant emission per unit product      0.1069  0.1154  mass of pollutant/mass of product

-------
             Conclusions - Flowsheeting
Demonstrated Capability of Advanced Process Analysis System
 - process flowsheet!ng
 - on-line optimization
 - pinch analysis
 - pollution assessment
 - chemical reaction analysis determined
  best alkylation reaction kinetics

Process Flowsheeting
  76 process units, 110 process streams
1,579 equality,  50 inequality constraints, 1,634 variables
Simulation validated using plant data and data reconciliation
Simulation predicted the performance of the plant
  within the accuracy of the data

-------
     Conclusions - Economic Optimization

Evaluated six operating points

25% to 215% increase in the profit

Increase  of  145% included
     8.5% reduction in costs and 2.2% increase in sales
     5.5% more olefin charge
     98% reduction in isobutane purchase cost
     7.2% reduction in feed to the Sat Deisobutanizer
     2.2% increase in the alkylate
     2.2% reduction in the sulfuric acid consumption.
     1.0% reduction in energy to 1888 MJ/min

-------
  Conclusions - Pinch Analysis and Pollution
                 Assessment

Pinch Analysis
 7.7% reduction in steam to 67x109 BTU/yr
 6.0% reduction in cooling water to 106x109 BTU/yr

Pollution Assessment
Demonstrated ability to locate and estimate the
severity pollutant emissions from the process.

-------
           Conclusions - Summary
Development and validation of process simulation
     most difficult and time consuming part
     of applying the System

Applicable to small plants

Typical improvements
     5% for on-line optimization
     5 -35% for pinch analysis
Detailed understanding of process
     - most valuable result
     - difficult to measure value
Program and users manual downloaded from
     'www.mpri.lsu.edu - no charge

-------
Studies on the Purification of nonwater
     Media by ceramic membranes

  Kagramanov Gueorgui G., Choupis
               Roman A.
D.I.Mendeleyev University of Chemical Technology of Russia
      125047, Miusskaya Sq.9, Moscow, Russia
    E-mail: sark@muctr.edu.ru ; kadri@muctr.edu.ru
      tel/fax: 7-095-978-82-60; 7-095-200-42-04

-------
    Production  and  applications  of the  ceramic
membranes (CM), modules and units, based on these
membranes, demonstrate the stable rise  in Russia.
Due to the unique properties of the CM- chemical,
microbiological  and  thermal  stability, mechanical
strength,  possibility  of  regeneration by rigorous
media  (acids, alkali  solutions) and  back-washing,
long life-time etc.- they are being employed  in many
branches of industry and life.
    These  advantages   of  CM,  compared  with
polymeric membranes (PM)- showed the way of their
successful application- to replace the  PM in the
filtration   systems   in    food,   microbiological,
pharmaceutical branches of industry, potable water
treatment systems etc., as well as in processes with
rigorous technological parameters, using aggressive,
abrasive    and    highly-viscous    media,    high
temperatures,  i.e. in  production of 'clean products'
by 'clean processes'.

-------
   The great  majority of the  commercialized
technologies using CM deal with  water media-
filtration of various biomasses in  production of
vitamines,   antibiotics,   lizine,  purification  of
enzymes,  treatment of milk and corresponding
milk  products, syrops and wines,  purification of
potable, mineral and waste waters  etc.
   The filtration   processes  and  technologies
dealing with nonwater systems, such as various
industrial  and vegetable oils, different kind of
fuels (gazoline, Diesel) are  developing, but not
commercialized yet.

-------
The  application of CM in these, environmentally
friendly,  processes  seems  very promising  and
prospective, permitting:
to regenerate and recycle  industrial and motor oils,
preventing pollution;
to develop  new  technologies  of natural  (mostly
vegetable)  oils' purification  instead of traditional
processes,  demanding  high  values   of  energy
consumption  and  producing  various  kinds  of
wastes;
to purity various types of fuels, especially Diesel
one,  from  mechanical   and  colloidal  particles,
including raisins and sulfur compounds, in order to
rise  the  engines  degree  of  combustion  and
decreasing pollution.

-------
  Table 1. Characteristics of MF ceramic membranes made of a-
AI2O3 (substrate) and coated by a-AI2O3 or ZrO2. Length 800-900
      mm, Porosity: substrate 40-45 %, selective layer 40%.
Numbers of
channels
1

1

7

19

Geometry
of membrane elements
Diameter,
mm
8*6

10*6

22

29
(spanner)
Channel
diameter,
mm
6

6

4

3.8

Pores diameter, mem
Substrate
3-5

4-6

5-10

10-15

Selective
layer
0.8-1.0
0.2-0.4
1.0-1.5
0.2-0.4
1.0-1.5
0.2-0.4
1.5-2.0
0.2-0.4
Distilled water
permeability,
m3/(m2*h*bar)
4.8-5.6
2.0-2.2
4.8-6.2
1.8-2.0
4.4-5.4
1.8-2.0
4.4-5.0
1.6-1.8
    Length 800-900 mm, Porosity: substrate 40-45 %, selective layer 40%.

-------
 Table 2: Characteristics of UF ceramic membranes with a-AI2O3
               supports. Pressure difference 1 bar.
Selective
layers
material

SiO2

ZrO2

TiO2

Mean pores
diameter,
nm

70
15
3
70
30
15
70
25
7
Perme
m3/(
Distilled
water

145
100
50
400
250
150
610
320
55
ability coefficient,
m2*h*bar) HO3
SiO2
sol

40
25
12
50
30
15
57
35
15
PVP,
M=40000
g/mol
58
47
32
110
78
60
90
65
35
Selectivity, %
SiO2 sol

98.0
99.2
99.9
98.9
99.1
99.1
97.5
99.3
99.4
PVP,
M=40000
g/mol
98.9
99.3
99.6
66.0
81.5
83.6
72.5
83.2
89.9
 The solution tested (table 2) were:
 SiO2 sol with solid phase particles of 30 nm diameter, concentration of S/O2- 5% weight
 Water solution of PVP (1% weight) with molecular mass of 111-360000

The corresponding experimental parameters and  data of filtration processes
using CM, (some characteristics of CM used in experiments are presented in
tables 1 and 2) in laboratory and pilot scales are presented and discussed.

-------
         NATO/CCMS Pilot Study on Clean
            Products and Processes
  7BQAM 72V£S /^0« 7WF 5FA4PX TTON
OF ORGANIC ACIOS AS EXAMPLES OF
     PROCESS INTENSIFICATION
              Jose Coca Prados
      Department of Chemical & Environmental Engineering
              University of Oviedo
          6th Meeting, Cetraro, Italy, May 14, 2003

-------
      Outline
Introduction
Reactive L-L extraction
Freeze concentration
Electrodyalisis

-------
t* f
NATO/COMS Pilot Study on Clean
  Products and Processes
 INTRODUCTION

-------
Strategies for process development
    Process integration:optimize energy resources

        S Heat exchangers (Pinch analysis)
        s Mass transfer networks
    Process intensification

        s  Equipment
        S  Processes

-------
•v jr
NATO/COMS Pilot Study on Clean
   Products and Processes
ORGANIC ACIDS

-------
             Organic acids
 Additives in food industry, chemical feedstocks

 Competition between microbiological and chemical
processes

 Low concentration when electrochemical or
biochemical routes are used

 Recovery from fermentation broth: precipitation as
Ca2+ salts and treatment with sulfuric acid

-------
Lactic acid as example of organic ac
            Fermentation
                    Esterification
                      As a Substitute
                      of other Toxic
                      Solvents
           Lactic Acid
                       Lactic Acid
  Food
Additives
                                       Polymers
Solvents and
Chemical
Products

-------

    NATO/CCMS Pilot Study on Clean
       Products and Processes
REACTIVE LIQUID LIQUID
       EXTRACTION

-------
Reactive liquid-liquid  extraction  (RLLE)
        Physical interaction solvent-feed:
        - solvent easily regenerated
        - low separation selectivity

        Chemical interaction solvent-feed:
        - difficult regeneration -^ reversibility
        - high selectivity

        Liquid-liquid extraction is suitable for:
        - Systems with low volatility
        - Removal of low volatility components from water
        - Removal of low-volatility polar compounds from organics
        - Recovery of thermally sensitive components

-------
Process intensification of RLLE


- Extractant impregnated resin (EIR)
  technique:
   • Advantages of solid adsorbent and a reactive
    extractant
   • Fixed or afluidized bed

- Extractive  ultrafiltration (EU)
- Pertraction

-------
   xtractive ultraf iltration
          Conventional Extraction
FEED (w)
SOLVENT (o)
                                  EXTRACT (o)
                     SETTLER
                                  RAFFINATE (w)

-------
    xtractive ultraf iltration
FEED (w)
SOLVENT (o)
      MIXEI
            EMULSION
                    Ultrafiltration
                       MEMBRANE
                                       EMULSION (w+o)
                                     RAFFINATE (w)

-------
 xtractive ultraf iltration
        Experimental set-up
FLOWMETER
                     BYPASS
      PERMEATE OUTLET
       MEMBRANE MODULE
        Q
                CENTRIFUGAL PUMP

-------
 Valeric  acid  recovery  by pertraction
                                                     Manometer
                                                     (input fibers)
Rotameter  :
                                     Manometer
                                      ((shells)
                 Module of
                 hollow fibers
                  Manometer
                  (output fibers)
                                                            Rotameter
                                       Manometer
                                       (output fibers)
            Module of
            hollow fibers
                                             Valve
                                                             Pump
    Aqueous feed
Organic phase
Reextractant

-------
*+ <»*
    NATO/COMS Pilot Study on Clean
      Products and Processes
FREEZE CONCENTRATION

-------
freeze concentration
1
feed
r
CRYSTAL
NUCLEATION
i
r
CRYSTAL
GROWTH
i
Crystal s
r
SEPARATION
T
              Degree of concentration
              = f (amount of ice frozen
              in product stream)
              Mass-balance:
                  w- — I —
                         C
f
                          C;
  concentrate

-------
      Freeze concentration
Advantages:
 - Low energy consumption
 - No scaling and fouling
 - Concentration of thermally sensitive products
 - Low corrosion
Disadvantages:
 - Limited concentration can be attained. 40-55 %
 - Higher capital and operating costs
 - Loss of product during ice separation

-------
Freeze concentration equipment
       Refrigerant outlet
       temperature
           cnulatng
           rufnj
           batti
        Refrigerant Inlet
        temperature  solution
                  outlet
Solution Inlet
tempera tuna
II a • u • , • •_•_;;_•_• B • 111 • U • • ^^^ ff
\l  L  Z^ J
  Peristaltic

-------
Reverse Osmosis-Freeze concentration for the
	Removal of Valeric Acid	


            Selection  of alternatives

            • EFFLUENT CHARACTERISTICS
                 Valeric acid concentration: 6000 ppm
                  30000 kg/h
                 Other compounds present:
                      other carboxylic acids < 200 ppm
                      degradation products
                      toluene 50 ppm

            • ALTERNATIVES
                 Reverse osmosis
                 Freeze concentration
                 Extraction (Physical and/or reactive)
                 Extractive ultrafiltration
                 Adsorption

-------
Reverse Osmosis-Freeze  concentration for the
  Removal of Valeric Acid:  Economic Analysis
      100
1000
10000   100000
       Plant capacity (kg/h)
100
1000   10000  100000
                      Plant capacity (kg/h)
• RO «
• FC

-------
*+ Q*
 NATO/COMS Pilot Study on Clean
   Products and Processes
ELECTRODYALISIS

-------
              ectrodyalisis
Reduction of the ionic content of a solution by

 - Potential difference

 - Ion-exchange membranes
      Membrane

    KXXXXXI
              Positive Ion
              charge
   (a) Cation exchange
     membrane
  Membrane

KXXXXXI
          Negative tan
(b) Anton exchange
  membrane

-------
                   ectrodyalisis  ce
                 Anode rinse
                  solution
Salted solution
       Anode
               O
Na
                       Cl
                     Cathode rinse
                     solution
Na
                            Cl
                                 I
Cl
^—-


Na
              Na
                                         Na
                                          Cl
                           L
                             Unit cell
           Anion-selective membrane
           Cation-selective membrane
                              Desalted product
                             O
                           •Cathode
                                                       Feed

-------
Applications
trodyalisis
 - Production of potable water from brackish
   water

 - Treatment of industrial effluents
   Demineralization of certain products
    • Chemical
    • Food
    • Pharmaceutical industry

-------
Electrodyalisis with bypolar membranes
   Water splits into H+ and 01+ ions

-------
Synthesis  of salycilic  acid with  bipolar membranes
                       Na  CO2
                          130 °C, pressure
                             H    H2S04
                                      OONa

(Phenol)   (Sodium Phenolate)     (Sodium Salicylate)
                                                 (Salicylic Acid)  (Sodium Sulphate)
                                          ED
                                                   t
                               Depleted SANa Solution
                     NaOH
                             t
                             BPM I  CEM I AEM I  BPM
                                      Salt
                  G	  H+
                Cathode  '
                          t
                        Electrode
                         Rinse
                        Solution  NaOH
                                         OH'	O
                                            '  Anode
                                     SANa
                                        Electrode
                                         Rinse
                                  SAH   Solution
                                           Na2SO4

-------
i Last visual aid !
   Thank you!

-------
        NATO CCM S Pibt Study on Clean
             Products and Precedes
              Cetei2D,Ita]y,2003
                                   odelLhg
and M edifying Packed B ed R eactors
   AntoiJoM artins, Paulo Laranjeira, M adalena D :ias, Jose C aribs L opes
 LAMftATBWttr OT BCftAfiWTiON AND RtACTtOW

-------
             Pzesentatbn Plan
Process latmsdrjcation: Definition  and  interest to
packed bed reactors.

N etw ork and geom etricalm odelof a packed bed.

Flow m odeHhg in packed beds.

M ass transport and reaction in a a packed bed reactor.

C onclisJons and possible m edifications of packed bed
reactors.

-------
            Piocess ZatmsafJcatbri

Process latensoficatiDn is a strategy to increase the efficiency
of process un±s, for exam p]e by reducing the raw m aterdals
or the energy consum ptbn of the process.
This goal  can be  reached  on]y  by  m edifying existing
processes or the developm en t of new ones.
 D esp±e the in portance of process JntensifiratiDn, both from
 econom deal and envdronm ental poiit of vJew , dt has been
 applied on a 1m dted scale.

-------
           Process ZatmsdtJcatbn
Process intensification can be in plena en ted in differentw ays
 Using different types of un±B,eg.,m embranes.
 The developm ent of different process: different chem ical
 pathways (G reen Chem istry),m u11~ifiinctbnalreactors,etc.
  P rocess integration.

-------
           Process Interi;
 Process intensiEicatiDn m ust look ID the alLprocess and not only
 to an aHun±s, as their depend on each other.
In p]em entation can be hindered by the costs of new equipm ent
and the ddsposalof old one.
The analysis of the benefits and tradeoffs of process
ihtmsification  m ust  be  based   on  a  detailed
understanding of the physicalphenom ena occurring
and their influence on the behaviour of the process.

-------
           Piocess Intent

A t the "heart' of aln ost any chem deal process there ds a
reactor. Process dntensifiratbn w dHhave m ore in pact closest
to the core of process ds applied.
                            Depending   on   type   of
                            reactdons, catalyst, chem deal
                            pathw ays  and   reactants,
                            m any types of reactors are
                            used.

-------
           Process Interi;
Packed bed reactors are advantageous in m any oases
                          No loss of catalyst.
                           Ensure a high surface area for
                           reaction.

                           H jgh conversion and selectivity
                           possible.
                     W ide range of operating conditions.
                    Enhance m ixture betw een reactants.

-------
Process latmsjfjcation:  Definition and interest to
packed bed reactors.

N etw ork and geom etricalm odelof a packed bed.

Flow m odeHhg in packed beds.

M ass transport and reaction in a a packed bed reactor.

C onclisJons and possible m edifications of packed bed
reactors.

-------
        N etwork-G eon etricalM odel

A network m odel was selected to describe the void space
between the particles.
  Real structure
                         Sm p.
N etw ork S tzucture

-------
       N etwork-G eon etricalM odel
M ann assum ptbns
Two types of elan en ts are used
   cham bers/spheres, characterdsed by
   Ghanne]s/cy]±Lders, charac±erdsed by Q and

-------
       N etwork-G eon etricalM odel

The  network  is  generated  by  repetition  of
fijndam entalunJtceH.
 C ham ber
and
channel
dJam eters fblbw  given  size
ddstrdbutions.
Local structure of network can be varJed by ran oving
channels and cham bers or changing relative size elem ents.

-------

-------

-------
       N etwork-G eon etricalM odel


The netw ork elem ents size distributions are functions of
porosity and particle size distribution.
  Assam ing

-------
         N etwork-G eon etricalM odel

 Average valies depends only on the porosity of the
 packed bed.

 If the particle size distribution is known
Average size  of the  network  elements predicted  using  the
geom etrical m odel  com pared w elL w ith  experin ental valies
obtained in packed fbrm ed w ith particQes w ith a narrow particle
size distribution.

-------
Process latmsjfjcation:  Definition and interest to
packed bed reactors.

N etw ork and geom etricalm odelof a packed bed.

Flow m odeHhg in packed beds.

M ass transport and reaction in a a packed bed reactor.

C onclisJons and possible m edifications of packed bed
reactors.

-------
                 F ]QW M odelbhg
F low ism odelled using the analogy w iih an elec±ricalcircuit
 If the resistance in each channel ds know n, the pressure and
 the flow fields are obtained by solving a non-linear, sparse
 system of equations.

-------
                F ]QW M  odelbhg
  T otal resistance of a channel ds the sum of three term s:
R .f - fractional resistance, function of the R eynolds num ber
 >Lam inarflow  - PodseuHle eq.
  Turbulent flow -Blasiiseq.
 >T ran sifbn zone - interpolation

-------
                   F ]QW M odelbhg
  !.^L and R^  - additional resistance due ID the connections
betw een channels and cham bers.
        -Linear flow  (K op Ik, 1982)
  R ±   -N onlinear flow  . B ased on the usualm ethod to calculate
  the pressure losses in accidents in pipe systm s. C onstants w ere
  gi/en to the sin ulator.

-------
W ihoutR ,  and R
        ]       ]    Eigun-25%

-------
                              mAN (1- e)
                             A 2 *APD e
F* - Piedncted
F* -Experimental

-------

-------
      M ass T zanqoortand R eaction

The m ass transport and reaction m odelrhg in a packed bed
reactor w as done for transient and steady state conditions.

 The m ass balance equations were written for the network
 elem ents assum ing:


   • Perfect  mixture  in  the  chambers. Accounts  for  the
     dispersion of m ass.
    Plig flow in the channels. Accounts for the convection of
    m ass. M athem atically represents a pure delay.

-------
      M ass T zanqoortand R eaction
A din ensionalm ass balance equations are:
                                      Chambers
                                      Channels
W hen solving the equations, delays w ere incorporated in the
cham bersm ass balances and considered explicitly.

-------
       M assTiansportandReaction
Proposed m odel has several distinct features from norm al
used m ode]s for describe m ass transport and reaction.


   • D elay due to the flow  of fluid ds taken in to account
    explicitly.
    D ispersive behaviour is m odelled directly using the local
    structuraland flow field characteristics.
    N o necessity to define param eters to determ ine from
    correlations or experim entaldata.

-------
       M a^Tian^ortandReaction

Different types of perturbations can be considered, both
uniform and non ^uniform , in time and space. Tine and
spatialevolition fora localstep perturbation is shown.
                     = 060
                                     . = 15

-------
          M assTian^ortand Reaction
D iOerent types of operation can be
studied easily. Example represents
the response to a  periodic pu]se
perturbation w in reaction.
                                     The influence  of  the  local
                                     structure ii  m ass transport
                                     can  be visualised. Example
                                     com pares a case w in bottom )
                                     and w ihoutchem deal reaction.

-------
       M assTian^ortandReaction

V arying  the  geom etrical  param eters of  the  netw ork
elem ents, it is possible to control the relative in portanoe of
the tw o m ass transportm echandsn s.
       25
       20 --
       15 --
       10 --
        5 --
                    12
                    125
                    15
                    1.75
         0.75
0.85
0.95
1.05
1.15
1.25

-------
       M ai^Tianqoortand Reaction
In steady state conditions the influence of the reactant
to the reactor can be studied in detail.
                   	^_
                              C oncentratbn   profiles
                              show n for a second order

                              different feeding m odes
                              of B .
E ffects of m ixture  and
segregation can be easily
studied.

-------
        M a^Tian^ortandReaction

C onditions to obtain optim al selectivity can be determ ined
from sin illations, avoiding costly and lengthy experin ents.
 o.s
 0.6
 D.-l
 0.2
        Do-tOO
      Da* 10
   a-0.75
   a - 0.38
   « - 0.01
          10
21)
        number of injection
The yield of S as function of
reaction,  feed   and  local
structure characteristics is
presented in  the figure  for
the kinetic schem e

-------
Process latmsjfjcation:  Definition and interest to
packed bed reactors.

N etw ork and geom etricalm odelof a packed bed.

Flow m odeHhg in packed beds.

M ass transport and reaction in a a packed bed reactor.

C onclisJons and possible m edifications of packed bed
reactors.

-------
                   C onclisbns
G eom etrical characteristics of the packed bed are
the controlling factor of is behaviour.
 M odel provides a good description of the hydrodinam ical
 behaviour.

 The  influence  of  the   local structure,  flow  field
 characteristics and operation conditions or the behaviour
 can be predicted.
 Data  required  is  easily  obtained  and  does require
 experin ents.

-------
                  C onclisbns

Proposed  m odel  is  predictive  and  uses only
inform ation of the packed bed structure.

Advantages:

 • R eduction on the design and developm ent stage.


 • E asier scale^up.
  C hanges can be addressed fester.

-------
                    C onclisbns
Possible extensions of them odel:
  Inclusion of the heat effects and is influence on the flow ,
  m ass transport and reaction in a packed bed reactor.
  Inclusion of m ass transfer betw een phases and adsorption
  C hem dcalreaction in the solid and fluid phase.

-------
                   C onclisbns

M edifications of packed beds rely on the control of
fbw and the m ixtiire of reactants at the local level

E xam pies include:


 •Use of packings ii  other types of reactors, eg. Bubble
 C olim n R eactors.

 •Structured packings
   M icrofluidics system sfbrbiochem icalorchem icalanalysis.

-------
New Technologies for Improving Gas-Liquid Transfer Processes  and

Catalytic Reactions


                            A.Criscuolil, E. Driolilj2

1 Research Institute on Membrane Technology (ITM-CNR), Via Pietro Bucci Cubo 17/C, 87030 Rende (CS)
Italy
;'2 Department of Chemical Engineering and Materials,  University of Calabria, Via Pietro Bucci Cubo 17/C,
87030 Rende (CS) Italy
      First meeting of the NATO/CCMS Pilot Study on Clean Products and Processes- Phase II

                              Cetraro (Italy) May 11-15 2003

-------
                    Aim of the contribution:
To discuss the role of some membrane operations in the logic of the Process




Intensification

-------
  Main targets of the Process Intensification

  To develop systems of production with:
- lower equipment-size/production-capacity ratio
- lower energy consumption
- lower waste production
- higher efficiency

-------
ITM
                     Content

                     Water deoxygenation
                     Sparkling water production
                     Hydrocarbons removal from aqueous streams
                     Catalytic reactions

-------
ITM
                         Water deoxygenation
The water deoxygenation by membrane contactors is successfully adopted by the




semiconductor industry because  of the high removals  achievable (dissolved




oxygen in the treated water less than 1 ppb) and low size.

-------
Liqui-Cel
!A«rmb
                         tacto
                                                      4 X 28 EXTRA-FLOW PRODUCT DATA SHEET
100 -
95 -
' 90 -
5
+ &5 -
2
- ftO -
' 75
i 7S

fin -
3 5 10 15 20 25 3O

•^^






0 1

~~---
^- ^






.1 2.
Water
.__
~~~--
"^-^


•---___ N? Sv/ee p
*w_
50 torr ^**^^^








3 3.4 4.
^^_
-^,
^^






^----_^
•^^^
^**^.


5 5.7 6.
8
Flow Rate (mi''hrj
                                                           1CO
                                                         S
                                                         c.
                                                         *
                                                        ot
                                                         CH
                                                        O
                                                                   — Wiit&r Flow Rate (cjpm}	

                                                                    5     10    15    20    25
                                                                              Two
                                                                              One Contactor
1.1
                                                                         2.3
                                                                               3.4
4.5
                                                                    Water Flow Rate (m
5.7
6.8
                                                             Test Conditions: Air Vaoj um Combo. 1 5O torr at 25 "C
V^illt1! 1 K'W l-vtllf 1, yfJMII
0 5 10 15 3D 25 30
•\^ J-. <-.n
— 12 .
n
- 10 -
m.
5 B -
* fi
t
5 4 .
A
0 .-,
11 0 .
[






J
) 1






,— - *•
.1 2.
UV:-it^r




Sh«
__^'
^^




Jlside
****^




_fff
^




s

-------
ITM
                    Sparkling water production
       C02, 02
C02
       Water, O2
                       Membrane Contactor
Water, CO2

-------
  ITM
            Comparison between traditional and proposed systems

Equipment cost (Euro)
CO2 consumption (kg/h)
CO2cost(Euro/h)***
CO2 in the atmosphere (kg/h)
Membrane replacement (Euro/y)****
Volume (m3)
Traditional
Deareation unit: 71,013
Saturation unit: 103,291
Total: 174,304
Deareation unit: 60
Saturation unit: 130**
Total: 190
30


3
Proposed
77,800*
110
17
60
25,900
0.25
Trad./Prop.
2.24
1.73
1.73



                             2
 A membrane cost of 92,96 Euro/m has been considered
** For saturating at 4.3 g/l 30 m /h of water, 130 kg/h of CO 2 have to be used.
*** The CO2 cost is of 0.155 Euro/kg
**** Membrane life-time: 3years.
                                  A. Criscuoli et al, Annals of New York Academy of Science, in press 2003

-------
  ITM
In desalination,  the content of oxygen  and carbon  dioxide  in  the  seawater
considerably affects the performance and the material life of the desalination
plants. Carbon dioxide also affects the pH and the conductivity of the water.
Removal of these gases is usually made by stripping in a packed column and
the final water pH is  adjusted by means of caustic soda. This operation is
difficult to fine control - due  to  the very low dosing rates- and is not well
accepted by end users who do not prefer chemically treated waters.

-------
  ITM
Membrane contactors working on the reverse osmosis permeate can efficiently
lead to the desired control of the oxygen and carbon dioxide content avoiding
the final use of chemicals.
The  membrane contactor unit does not  increase the  energy consumption
because it operates at atmospheric pressures and allows to strongly reduce the
environmental pollution.

-------
ITM
             Hydrocarbons removal from aqueous streams
       Exit gas stream
Stripping phase (air/ethane)
       Water, HC
                         Membrane Contactor
    Water
                      P. Bernardo et al., submitted toClean Processes and Environmental Policy, 2003

-------
ITM
             Hydrocarbons removal from aqueous streams

Traditional process:    Stripping towers/ steam     Removal: 90%

Membrane contactors:  Air/ethane as strip phase    Removal: 90% - 99%
                                                       (35°C) - (70°C)
Main advantages of the new operation:
             -  higher removals
             -  no need of high quantities of steam
             -  reduced size
                      P. Bernardo et al, submitted toClean Processes and Environmental Policy, 2003

-------
  ITM
Membrane operations can be applied also for reaction purposes, each membrane
pore acting like a "micro-reactor".
                     Products, un-reacted reagents
             Catalyst
                             Reagents
                Membrane pores like "micro-reactors"

-------
  ITM
If the membrane is high selective for the product of interest it is possibile to
recover it directly at the permeate side, without the need of separation units.
By using membrane reactors it is possibile to  obtain higher conversions  or
selectivities with respect to traditional reactors and the same performances of
conventional apparatus can be achieved with lower energy consumption

-------
  ITM
In catalytic membrane reactors it is possibile to combine the reaction step to the
separation one, performing two different operations into a single device.
                                      Membrane selective to the desired product
                       Desired product
        Reagents       *   o°°o oo0o0o     Products, un-reacted reagents
               Catalyst
                Reaction and separation in a single device

-------
  ITM
By using membrane reactors it is possibile to achieve the same conversion of
traditional devices at lower temperatures.
As a consequence, the reaction selectivity can be improved by mimimising
side reactions and limiting the amount of carbonaceous deposits.

-------
ITM
                    Equilibrium-limited reaction
                HoO+CO = COo+Ho      AH=-40.6 kJ/mol
            The equilibrium constant decreases with temperature:
                        Kp=exp[(4577.8/T)-4.33]

-------
  ITM
The  water gas shift reaction  is present in  several industrial processes such as the
ammonia and hydrogen production.

Hydrogen is mainly produced by steam reforming or partial oxidation of hydrocarbons.

However both processes lead to  mixtures of hydrogen and carbon monoxide that can not
be directly used for industrial applications.
For example, for the  ammonia production the  carbon monoxide concentration has  to be
very low in order to avoid the deactivation of catalyst.
The water gas shift reaction is used, in this case, for  reducing the CO concentration and
for producing more hydrogen.

-------
  ITM
Reactors used for carrying out the water gas shift reaction are usually adiabatic.
The reaction is  firstly carried out in a reactor with iron-based catalyst (High
Temperature reactor-HT) and, after a cooling stage, the exit stream is fed to a
reactor with copper-based catalyst (Low Temperature reactor-LT).

-------
  ITM




                              CASE STUDY





The WGS reaction was carried out both in a fixed bed reactor and in a tubular



palladium membrane reactor.
                              Stainless steel tube




    Reagents                       //     Products, un-reacted reagents
                                Q0o0o°o 8 o
           Catalyst




                           Fixed bed reactor

-------
  ITM
                          Palladium membrane
Ceramic mesoporous membrane
       Reagents
frw-^^w^^^^
o  o ^ o _O_OOOQ  o 0
                          0
                                   oo

                  Catalyst"
Products, un-reacted
reagents
                        Palladium membrane reactor

-------
 ITM
   100



   90 +
^ 80
C
o
   70
> 60
c

O 50

O
O 40
   30 +



   20
                       Fixed bed reactor



                       Palladium

                       membrane reactor

                       Equilibrium
      0
10
15
20
    Time factor (-103 g-cat.-min-(CO mol)'1)

-------
  ITM
Comparison between traditional  devices  and the palladium membrane reactor -PM-
(palladium thickness, 75 |um) [A. cnscuoit etai, j. Mem. Set. isi/i (2001) 21-27]
                             Reactors characteristics
                               HT
                LT
                  PM
           Volume (m )
 6.2
4.52
 5.97
          Catalyst (Kg)
4,500
1,000
4,885

-------
ITM
                            Capital Costs (Euro)
                                 Industrial plant
                         PM
          Reactors
77,440
 6.4-10'
           Catalyst
49,000
 15,762
        Separation unit
1.03-10'
            Total
1.16-10'
6.78-10'
                      Operating Costs (MEuro per year)
                                      2.43
                         6.97

-------
  ITM
                                 Conclusions
The  introduction of membrane operations  in industrial  cycles  might represent  an
interesting way to realize the rationalization of chemical productions in the logic of the
Process Intensification.
Membrane  contactors are high efficient systems for carrying  out  the mass transfer
between  phases and  achieving  high removals. They also present lower size than
conventional apparatus.
Membrane  reactors, although not already present at industrial  level, represent  useful
systems to improve chemical reactions yield and to enhance the performance of chemical
productions.

-------
 ITM - CNR
Istituto per la Teciralojia delle Membrane '
NA TO CCMS Pilot Study on Clean Products and Processes
                  2003 Annual Meeting
               Hotel San Michele, Cetraro
     Rationalisation of productive cycles in the
    agro-food industries by innovative processes


                 A. Cassano, E. Drioli

         Institute on Membrane Technology,  ITM-CNR,
        c/o University of Calabria, via P. Bucci, cubo 17/C
                 l-87030Rende (CS), Italy
               Phone: +39 0984 492011-492014
                  Fax: +39 0984 402103
                E-mail: a.cassano@itm.cnr.it

-------
  ITM - CNR
 I Istituto per la Teciralojia delle Membrane '
Fruit and vegetable juices  are  beverages of high
nutritional value since they are enriched with minerals,
vitamins  and  other  beneficial  components for human
health  that are  generally  indicated  as  antioxidants.
Unfortunately  during  the  industrial  transformation,  a
large part of the characteristics determining the quality of
the fresh  product undergoes  a  remarkable modification:
the thermal damage  and the chemical oxidation degrade
more sensitive components reducing the quality of the
final product.

-------
  ITM - CNR
 I Istituto per la Teciralojia delle Membrane '
  Fruit juices
present on the
    market
                           simple squeezing and
                               then submitted
                           to a mild pasteurisation
FC, not from concentrate juice
freezed just after squeezing
                     , juices reconstituted from concentrat

-------
 ITM - CNR
I Istituto per la Teciralojia delle Membrane '
 The production of concentrated fruit juices is of interest
 at industrial level since they can be used as ingredients
 in many products such ice creams, fruit syrups, jellies
 and fruit juices beverages.  Furthermore,  fruit  juices
 concentrates, because of their low water activity, have
 a higher stability than single-strength juices.
 In addition, package, storage  and shipping costs are
 remarkably reduced.

-------
  ITM - CNR
I Istituto per la Teciralojia delle Membrane '
 When the concentration is carried out by EVAPORATION,  most of
 the aroma compounds contained in the raw juice are lost  and  the
 aroma profile undergoes an irreversible change with a consequent
 remarkable qualitative decline.  Besides, the  heat required to  perform
 the evaporation results  in some "cooked"  notes  recognised as  off-
 flavors.
 Commercial freeze concentration systems, in which water is removed
 as ice and  not as  vapor (CRYOCONCENTRATION),  permit  to
 preserve the volatiles during the water removal process but, they  are
 not able to  substitute far the evaporative concentration of products
 with large diffusion (i.e. citrus juices) since they require a  remarkable
 energy consumption. Besides the achievable concentration (about 40
 °Brix) is lower than the values obtained by evaporation (60-65 °Brix).

-------
 ITM - CNR
I Istituto per la Teciralojia delle Membrane '
MEMBRANE  PROCESSES  are today  consolidated
systems  in  various  productive  sectors,  since  the
separation process is athermal and  involves no phase
change or chemical agents. The  introduction of these
technologies in  the industrial transformation cycle of
the  fruit juices  represents one  of the technological
answers to the problem of the production of juices with
high quality, natural fresh taste and additive-free.

-------
 ITM - CNR
I Istituto per la Teciralojia delle Membrane '
 Ultrafiltration  membranes retain  large  species such  as
 micro-organisms,  lipids, proteins  and colloids while small
 solutes as for example vitamins, salts, sugars, flow through
 the membrane together with water. Therefore the possibility
 of  microbial  contamination  in the permeate  stream  is
 minimised   avoiding   any   thermal   treatment   and,
 consequently, loss of volatile aroma substances.
 Clarified juice coming from the Ultrafiltration process can be
 commercialised or submitted  to a concentration  process in
 order  to  obtain a product suitable for  the preparation  of
 juices and beverages.

-------
 ITM - CNR
I Istituto per la Teciralojia delle Membrane '
 The Reverse Osmosis  process permits  to separate principally
 water from the juice but it is limited by high osmotic pressures; it is
 used as a preconcentration technique which permits concentration
 values  of about 30 °Brix  corresponding to osmotic pressures  of
 about  50 bar. Aroma  compounds and other important chemical
 constituents  such  as  anthocyanins,  vitamins, sugars,  acids,
 calcium, potassium,  magnesium and phosphorus are rejected  in
 the process.
 The limitation of  high osmotic pressures can  be reversed  by
 continuing  juice  concentration  by  Membrane Distillation   or
 Osmotic Distillation.

-------
  ITM - CNR
  Istituto per la Teciralojia delle Membrane '
        INTEGRATED MEMBRANE OPERATIONS

The  introduction of membrane operation  units is studied
as a fundamental  step towards  the  rationalisation  of
traditional  industrial  processes  in  terms  of energy
consumption, of product recovery  and improvement  of
quality in agro-food productions.

The combination among each other of different membrane
operations   such   as  enzyme   membrane   reactors,
microfiltration,    ultrafiltration,    nanofiltration,   reverse
osmosis  and osmotic distillation, is studied  in order  to
identify  their synergistic effects on the  optimisation  of
processes for the production of fruit juices.

-------
 ITM - CNR
I Istituto per la Teciralojia delle Membrane '
The possibility to realise integrated membrane systems
in which all the steps of the productive cycle are based
on  molecular   membrane   separations   can   be
considered a valid approach for a sustainable industrial
growth  within the   PROCESS  INTENSIFICATION
strategy. The aim of this strategy is to introduce in the
productive cycles new technologies  characterised  by
low   encumbrance  volume,   advanced   levels  of
automation   capacity,   modularity,   remote  control,
reduced energy consumption, etc..

-------
  ITM - CNR
 Istituto per la Teciralojia delle Membrane '
New products from fruit and vegetables with high nutritional value
                           (PNR- Tema 2)
                         Duration: 36 months

                    Project Coordinator: PARMALAT

Aim of  the  project is the  development of new technologies for the
production of liquid foods from fruit and vegetable as alternative to the
traditional processes of the agro-food industry. An integrated membrane
process  for the clarification and  concentration of carrot and citrus fruit
juices is developed for the production of juices with high nutritional value
and high organoleptic quality.
             Funding Board      ^=>    MIUR
                      Istituto Mario Negri Sud; Parmalat - Centro Ricerche; San
Collaboration   * — )  Giorgio Flavors S.r.L; Emmegi Agroindustriale; Stazione
s                     Sperimentale     Industria    Conserve    Alimentari;
                      Tecnoalimenti S.C.pA; Universita  di Parma

-------
 ITM - CNR
Istituto per la Teciralojia delle Membrane '
  Blood orange juice, mostly Tarocco variety, were from Sicily (1999
  Production): the concentration of the raw juice was about 12.0-12.6
  °Brix with a pH of 3.5. Traditionally concentrated orange juice was
  produced by a multiple effect TASTE  (thermally accelerated short
  time evaporator) evaporator at a final concentration of 56.3 °Brix by
  Parmalat SpA.

  Lemon juice was from  Sicily (1999 Production): the concentration
  was about 7.1 °Brix with a pH of 2.8.

  Carrot juice was produced by chemical and physical treatment and
  it was supplied  in freezed packages  at pH  4.48  and  with a
  concentration of 6 °Brix.

-------
  ITM - CNR
 Istituto per la Teciralojia delle Membrane '
                   Ultrafiltration process

UF is most commonly used to separate a solution that has a mixture
of some desirable  components  and some that  are  not desirable.
Typical rejected species include sugars, bio-molecules, polymers and
colloidal particles.

The  driving force for transport across the  membrane is a pressure
differential (UF operates at 2-10 bar).
UF processes perform feed clarification, concentration  of rejected
solutes and fractionation of solutes.

UF membranes are capable of retaining species in the range of 300-
500,000 dalton of molecular weight, with pore sizes ranging from  10-
1000 Angstrom (103-0.1 jum).  These are mostly  described by their
nominal  molecular weight cut-off  (1000-100,000 MWCO),   which
means,   the  smallest  molecular weight  species for  which  the
membranes have more than 90%  rejection.

-------
  ITM - CNR
I Istituto per la Tecnologia delle Membrane '
     Clarification of citrus and carrot juice by uitrafiitration
 Juices were  submitted, without any preliminary treatment,  to a
 clarification process by UF using a laboratory pilot plant supplied
 by Verind SpA (Rodano, Milan,  Italy). The plant, with a 25 I feed
 tank, was equipped with a Koch tubular membrane module

       Type                       Koch Series-Cor™ HFM 251
       Configuration               Tubular
       Membrane polymer           PVDF
       NMWCO                   15kDa
       Membrane surface area       0.23 m2
       Average pores diameter       59 A
       pH operating range           2-11
       Temperature operating range  0-55 °C
       Pressure operating range	0.8-5.5 bar	

-------
  ITM - CNR
• Istituto per la lecnolqgia delle Membrane '
     [«
Ultrafiltration pilot pla

-------
  ITM - CNR
• Istituto per la lecnolqgia delle Membrane '
                                     T
                                     10
                                      11
                     UF laboratory pilot plant
                                                      7
           8
    1 - Feed tank
   2 - Feed pump
  3,6 - Manometers
4 - Membrane module
  5 - Thermometer
   7 - Cooling coil
 8 - Regulation valve
    9 - Flowmeter
    10 - Permeate
 11 - Digital balance

-------
 ITM - CNR
I Istituto per la Teciralojia delle Membrane '
Experiments were  carried out  according  to  the  total
recycle mode (recycling both permeate and retentate
stream   in   the  feed   tank)   and  to  the  batch
concentration   mode   (collecting   separately   the
permeate stream).
The total  recycle mode was used in order to measure
the permeate flux in different operating conditions and to
identify  the  optimal   operating  conditions  for  the
clarification process.

-------
  ITM - CNR
• Istituto per la lecnolqgia delle Membrane '
                              Retentate
Permeate
                  Feed
                 Scheme of the total recycle configuration

-------
  ITM - CNR
• Istituto per la lecnolqgia delle Membrane '
              Feed
                                                           Permeate
             Scheme of the batch concentration configuration

-------
 ITM - CNR
I Istituto per la Teciralojia delle Membrane '
              Effect of the TMP on permeate flux

   Permeate flux increases with pressure up to a limiting value
   (TMPHm) which depends on the  physical properties of the
   suspension  and feed flow rate. Any increase in pressure is a
   source of inefficiency, because the energy input increases for
   no increase  in  production rate.  Besides  beyond  TMPHm
   membrane fouling becomes increasingly important and the
   flux decline is accelerated.

-------
ITM - CNR


ou
28
26
^
^m
"
• ^L^T
•
a
-«•
I 22
Q.
•>
20
18
1R

i A A
* * • •
* * • .
'•***,**«.,..«,. .^










» TMP - 0 J.^ har
I IVIr U.H-U Udl
* TMP = 0.75 bar
• TMP = 1.05 bar
A TMP = 1,3 bar


 0
50
   100

Time (min)
150
200
                  Ultrafiltration of carrot juice
   Time course of permeate flux at different operating TMPs
          Operating conditions: T = 23.5 °C; Qf = 800 l/h
                                             &0/t<)6p/ie v/roieiefrndfi dif&ft Jfacesefte

-------
  ITM - CNR
• Istituto per la lecnolqgia delle Membrane '
           30
           25
           20
           15
           10
            0
             0
0.5               1

     TMP (bar)
1.5
   UF of carrot juice. Effect of the transmembrane pressure on the permeate
                                    flux
                 (Operating conditions: T = 23.5 °C; Qf = 800 l/h)

-------
  ITM - CNR
I Istituto per la Teciralojia delle Membrane '
          Effect of the feed flow rate on permeate flux

   The feed flow rate \s another important  parameter for the
   performance of  the  ultrafiltration  process.  The cross-flow
   velocity affects the shear stress at the membrane surface and,
   consequently,  the  rate  of removal  of deposited  particles
   responsible of flux decay.

-------
ITM - CNR
^^«
cs
s
E

-------
  ITM - CNR
• Istituto per la lecnolqgia delle Membrane '
          25
          20
       0)1  15
        £ 1b
          10
           0
            300
500
 700


Qf(l/h)
900
1100
       UF of carrot juice. Effect of the axial flow rate on the permeate flux

                (Operating conditions: T = 23.5 °C; IMP = 0.85 bar)

-------
 ITM - CNR
I Istituto per la Teciralojia delle Membrane '
          Effect of the temperature on permeate flux

  When the operating temperature \s raised the feed viscosity
  is  reduced and diffusion  coefficients of  macromolecules
  increase. The effect of these two factors is to enhance mass
  transfer and so increase the permeation rate

-------
      ITM - CNR
    I Istituto per la Teciralojia delle Membrane '
   24
   22
^ 20
es
 E
 =- 18
 1
 
-------
  ITM - CNR
• Istituto per la lecnolqgia delle Membrane '
           25
           20
           15
           10
            0
              12
17
 22

T(°C)
27
32
       UF of carrot juice. Effect of the temperature on the permeate flux
               (Operating conditions: Qf = 800 l/h; IMP = 0.85 bar)

-------
  ITM - CNR
• Istituto per la lecnolqgia delle Membrane '
                       50




tM
E
V
^
Q.





^.U
1
24 -
22 -
20 -

18 -

16 -

14 -

12 -
10 -
p

I
*••••
* • •
* •
' •





A
A A A * * A
^AAAAAAA


• JP
A VRF





A
AA
A ' •
A




A
A
A

A




•
•
••

1 U

- 8

- 6



- 4


- 2

n
  100        150

Operation time (min)
200
250
           UF of carrot juice. Time course of permeate flux and VRF
          (Operating conditions: T = 23.5 °C; Qf = 800 l/h; IMP = 1.03 bar)

-------
 ITM - CNR
Istituto per la lecnolqgia delle Membrane '
t.o
4
^ 3.5
(0
Q_
CM 3
E
T 2.5
"E 2
o
b 1.5 -
0.5
n
























































             before the     after the    after cleaning  after cleaning after cleaning
            treatment with treatment with  with NaOH  with Ultrasil 10 with enzymatic
             carrot juice    carrot juice      solution      solution      detergent
          Regeneration of water permeability in UF membrane module
                  (Operating conditions: T = 25 °C; vf = 0.09 m s

-------
 ITM - CNR
I Istituto per la Teciralojia delle Membrane '
               Advantages of the UF treatment

           reduction of clarification times
           removal of suspended solids and turbidity
           simplification of the clarification processes
           increasing of clarified juice volumes
           possibility to operate  at room temperature
        preserving the juice's freshness, aroma and
        nutritional value
        =^> possibility to avoid gelatines,  adsorbents
        and
        other filtration coadiuvant
           improvement of the productive process

-------
 ITM - CNR
• Istituto per la lecnolqgia delle Membrane '
            micro-organisms, lipids,
               proteins, colloids
  (retentate highly stable to heating treatment)
     pasteurisation
citrus juice
                               UF
            vitamin C, salts, sugars,
             aromatic compounds
    addition to
concentrated juices
  concentration
  (RO, OD)

-------
 ITM - CNR
Istituto per la Teciralojia delle Membrane '
             Osmotic distillation process

OD is a new membrane process also called "isothermal MD"
that can be used to remove selectively water from aqueous
solutions  under  atmospheric  pressure  and  at  room
temperature, avoiding thermal degradation

It involves the use of a microporous hydrophobic membrane
to separate two  circulating aqueous solutions at different
solute  concentrations:  a  dilute solution and  an hypertonic
salt solution.  The difference in solute concentrations, and
consequently in water activity of both solutions, generates, at
the vapour-liquid  interface, a  vapour pressure  difference
causing a vapour transfer  from the dilute solution towards
the stripping solution.

-------
 ITM - CNR
I Istituto per la Teciralojia delle Membrane '
The  water transport  through the membrane can  be
summarised in three steps:
     evaporation  of water at the dilute  vapour-liquid
interface
- diffusional or convective vapour transport through the
membrane pore
- condensation of water vapor at the membrane/brine
interface.

During the OD process the stripping solution is diluted
due to the water transfer from the feed stream. It can be
reconcentrated by evaporation and in this sense it can
be recycled and reused in the process.

-------
   ITM - CNR
 • Istituto per la lecnolqgia delle Membrane '
                         Increasing Water Vapor Pressure
<



Membra


r

••*
^-i
: i


Diluite
Brine Out


ne *"

\ — /
ttt
tt
t t
	 ^




V.
t
t
t
t
--—
f > f
^^•^•••^^•••wBvHH^Rpni
^""^>
Diluite

Feed In

— 1

tft
t t
ft
t t
X-" 	 >v
Brine In



^^ f >
^vav^^iBB^BttftflBKaaw- >
^-

1 ~^>
Concentrated
k Feed Out
                         Decreasing Water Vapor Pressure
Mechanism of osmotic distillation through a microporous hydrophobic membrane (Hogan et al., 1998

-------
  ITM - CNR
 Istituto per la Teciralojia delle Membrane '
The clarified juice  was  submitted  to  OD experiments  using  a
laboratory  plant  equipped  with  a  Hoechst-Celanese  Liqui-Cel
membrane contactor. The juice was recirculated in the shell side of
the membrane module; Calcium Chloride Dihydrate, recirculated in
the tube side of the  module, was used  as stripping solution. It was
chosen because it is not toxic, and it is ready available at low cost.
  Fiber Characteristics
  Fiber type
  Cartridge Operating Limits
  Maximum Transmembrane Differential Pressure
  Maximum Operating Temperature Range
  Cartridge Characteristics
  Cartridge Dimensions (DxL)
  Effective Surface Area
  Effective Area/Volume
  Fiber Potting Material	
Celgard® Microporous
Polypropylene Hollow fiber

4.2 kg/cm2 (60 psi)
40 °C (104 °F)

8x28 cm (2.5x8 in)
1.4m2 (15.2 ft2)
29.3 cm2/cm3
Polyethylene	

-------
  ITM - CNR
• Istituto per la lecnolqgia delle Membrane '
                 Brine solution (Tube side)
                                 7
 1 - Extracting solution tank
 2 - Brine pump
 3,5,7,8 - Manometers
 4 - OD membrane module
 6,9 - Flowmeters
 10 - Feedpump
 11 - Feed tank
 12 - Digital balance
                                          8
                      Osmotic distillation laboratory plant
    Juice
    (Shell side)
11
   o
12

-------
  ITM - CNR
• Istituto per la lecnolqgia delle Membrane '
             2.5"x8" LiquiCel module - Hoechst Celanese
                              - • •
                              Hollow f-'iher Membrane
Cartridge  Distribution Tube
Baffle  Collection Tube  Housing


-------
 ITM - CNR
Istituto per la Teciralojia delle Membrane '
•1 ~l
1 .1
OQ
.y
.8
n 7
U. /
Oc
.0
Oc
.O
0/1
.**
n ^
u.o
n o
A
AA
A
* AA
A
**, A
^ A
» A

••_ * • • ,
'••••••_ m
m m
• calcium chloride
• calcium chloride
» calcium chloride
A calcium chloride


k A
> A A
» A
* •
:•....
• •
dihydrate 30% (w/w)
dihydrate 40% (w/w)
dihydrate 50% (w/w)
dihydrate 60% (w/w)



A ,
* » • » • A * <
• : • d> . . • ,
    G)
                   20
40         60        80

  Operation time (min)
100
120
              Characterisation of OD membrane module with water
             (Operating conditions: T = 25 °C; Qf = 29.8 I rr1; Qb = 37.8

-------
  ITM - CNR
I Istituto per la Teciralojia delle Membrane '
             1 -
          D)
             0 -
                                                            - 60
                                                            - 50
                                                            70
                                                                D)
                                                               O
                                                               O
 - 40  ,2

      O


 - 30  I-
                                                            - 20
                                                             10
                         100         200         300

                             Operation time (min)
400
              OD of carrot juice coming from a sequence UF-RO
           Time course of evaporation flux and TSS concentration
    (Operating conditions: T = 26 °C; Qf = 28 I rr1; Qb = 69 I rr1; IMP = 0.13 bar)

-------
  ITM - CNR
I Istituto per la Teciralojia delle Membrane '
           1  -
o
^
                    50
                    100      150     200

                    Operation time (min)
250
                                                             70
                                                            - 60
                                                            - 50
                                                            - 40
                                                            r- 30
                                                            h.30
                                                            - 20
                                                            - 10
                                                                (O
300
            OD of blood orange juice coming from a UF treatment
           Time course of evaporation flux and TSS concentration
    (Operating conditions: T = 26 °C; Qf = 28 I rr1; Qb = 69 I rr1; IMP = 0.13 bar)

-------
  ITM - CNR
• Istituto per la lecnolqgia delle Membrane '
  BLOOD
 ORANGE
  JUICE
   UF
PERMEATE
    RO
RETENTATE
    OD
RETENTATE

-------
  ITM - CNR
 I Istituto per la Teciralojia delle Membrane '
                  TAA measurements
In the  traditional  concentrated  juice  (TC,  56.3  °Brix)  a
decrease of the antioxidant activity (20-25%) was measured
(6.85 ± 0.20 mM trolox), in  comparison with the fresh juice
(8.61 ± 0.07 mM trolox). During the ultrafiltration process TAA
was  maintained both for the permeate and for the retentate
(UFP 8.48 mM trolox; UFR, 8.52 mM  trolox). The subsequent
concentration treatment by osmotic distillation did not induce
other significant changes to TAA, independently from the final
concentration obtained: the highly concentrated sample at 61
°Brix still showed a high value of TAA (7.66 mM trolox).

-------
  ITM - CNR
• Istituto per la lecnolqgia delle Membrane '
                           8.48
8.52
                                                         7.66
                                                                       8


                                                                       7


                                                                       6 ?
                                                                         o
                                                                         o
                                                                       5 t


                                                                       4 I
                                                                         <
                                                                         <
                                                                       3 "-


                                                                       2
                                                                       0
          Fresh juice (12.0    UF-P(11.2     UF-R(13.5     OD (61 °Brix)
              °Brix)           °Brix)           °Brix)

               TAA variation in samples coming from a UF-OD sequence
                                                                              P

-------
  ITM - CNR
• Istituto per la lecnolqgia delle Membrane '
                Ascorbic acid measurements in samples of blood orange juice
                            treated by membrane processes
                                                             \
                                                                1000
                                                                900
                                                                800  _
                                                                700  Q.
                               600
                               500
                               400
                               300
                               200
                               100
                               0
                                                                     'o
                                                                     n
                                                                     u
                                                                     1
                                                                     o
                                                                     (A
                       TQ
UF-R
UF-P
OD

-------
  ITM - CNR
• Istituto per la lecnolqgia delle Membrane '
         Flavonoids in samples of blood orange juice treated by
                          membrane processes
               46.74      46.79
     46.76
     47.31
                     32.38
                     TQ
                                        33.65
                           50
                           45
                           40
                           35
                           30
                           25 (ppm)
                           20
                           15
                           10
                           5
                           0
UF-P
UF-R
OD

-------
  ITM - CNR
• Istituto per la lecnolqgia delle Membrane '
           Hydroxycinnamic acids in samples of blood orange
                  juice treated by membrane processes
          Fresh juice
UF-P
UF-R
                                                          60
                                                          50
                                      1 sinapico

                                      Iferulico

                                      I caffeico

                                      1 p-cumarico
                                                          40 £
                                                             Q.
                                                             ^

                                                             C
                                                             O
                                                          30 '-i
                                                          20 o
                                                           10
                                                          0
OD

-------
  ITM - CNR
• Istituto per la lecnolqgia delle Membrane '
        Anthocyanins in samples of blood orange juice treated
                        by membrane processes
                                                           70
                                                           60
                                                           50
                                         n cian-3-gluc

                                         n cian-mal-3-
                                          gluc
                                         n Antocianine
                                          totali
                                                           40 §
                                                              "+J
                                                              2
                                                           30 £
                                                              0)
                                                              o

                                                           20 §
                                                           10


                                                           0
        fresh juice
UF-P
UF-R
OD

-------
  ITM - CNR
 I Istituto per la Teciralojia delle Membrane '
UF and OD permit to preserve the TAA of the juice also in
highly concentrated samples (61 °Brix). Slight reductions
were observed for  the ascorbic acid and anthocyanins
whereas  the  other components  remained  practically
unchanged (hydroxycinnamic acids and flavonoids).  On
the  contrary,  a   very   high   degradation  of  these
components was observed in the  thermal concentrated
juice.

-------
  ITM - CNR
 I Istituto per la Teciralojia delle Membrane '
The  juice  concentrated with the  proposed  membrane
technology retain its bright red colour and large part of its
pleasant aroma, which is on the contrary completely lost
during thermal concentration.
Thus, this product is more similar to a fresh orange juice,
being  aroma,  colour and  natural  antioxidants  better
preserved during concentration.

-------
   ITM - CNR
  Istituto per la Teciralojia delle Membrane '
        Integrated membrane processes for clarification and
                    concentration of kiwifruit juice
  Research activities concerning the clarification and concentration of kiwifruit juice
  are in progress. Ultrafiltration is studied for the clarification of the raw kiwifruit
 juice. Studies on the identification of suitable membranes, the optimal operating
  conditions and feedpretreatment are in progress.
  The UF permeate is concentrated by osmotic  distillation. In this process the
  optimal operating conditions and the effect of these parameters on the evaporation
  fluxes are understudying.
  A pervaporation step for the recovery of aroma compounds from UF or OD
  streams is under studying. An integrated membrane process for the production of
  concentrated kiwifruit juice with high nutritional value will be developed.

„ „ ,     .         .	N    Citrus  Research   Institute,   Chinese  Academy  of
Collaborations     ^v    A  .  ,,   , 0  .       n  .,  .  ~,     .    ~u.
                      '    Agricultural Sciences, Beibei, Chongqing, China

-------
   ITM - CNR
  1 Istituto per la Tecnologia delle Membrane •
                          KIWIFRUIT PROPERTIES

i—S    Kiwifruit originates  from  an  indigenous  plant  of southern  China
       (Actinidia Chinensis)

       Italy  is  the  world's  largest  kiwi  producer  with  a  production  of
       about  300,000  tons/year  (33%  of  the  world-wide  production)
       and  a cultivation  area  of 19,000 hectares  distributed  mainly  in
       4 regions (Latium, Emilia-Romagna, Piedmont and Apulia)

       Kiwifruit is  the most nutrient dense of all  fruits  with  an index  of
       16 (daily value/100 grams)

       It   has  impressive   antioxidant   capacity,  containing  a  wealth  of
       phytonutrients   (carotenoids,   lutein,   phenolics,   flavonoids   and
       clorophyll

       Content in  sodium  and  fat is  very  low  (kiwifruit  contain  no
       cholesterol)

-------
  ITM - CNR
Istituto per la Teciralojia delle Membrane '
           Kiwifruit offers benefits for specific health conditions

=> CANCER (antimutagenic component helping to prevent genetic mutations)
=> DEPRESSION (inositol as  a precursor of an intracellular second messenger system,
can
be beneficial in the treatment of depression)
=> DIABETES (inositol may play a positive role in regulating diabetes)
=> EYE  HEALTH  / MACULAR DEGENERATION (kiwifruit is  rich in  phytochemicals,
xanthophylls and  lutein  that have  an important role in  the prevention  of  macular
degeneration)
=> HYPERTENSION (the sodium-to-potassium ratio is extremely favorable in kiwifruit)
=> IMMUNITY (kiwifruit is considered an immune booster due to its high level of vitamin C)
=> PHYSICAL FITNESS (kiwifruit  contains  a  wide  range of  minerals essential for
replenishing)
=> STRESS REDUCTION (high level of serotonin)
=> WEIGHT CONTROL (kiwifruit contains the best balance of nutrients per calorie)

-------
 ITM - CNR
I Istituto per la Teciralojia delle Membrane '
 For  all the above  mentioned characteristics and  other
 important  properties  (resistance  during  preservation,
 sensory characteristics,  etc.)  kiwifruits  have  a  great
 potential for industrial exploitation
 The production of concentrated fruit juices is of interest at
 industrial level since it reduces the storage volumes
 (reducing transport and storage costs) and facilitates
 preservation

-------
  ITM - CNR
I Istituto per la Teciralojia delle Membrane '
    20
    15
        ^^ki     L ^^ ^^A^^^^^n^^^^ 4|^   l^A^fe   *
          A?   ^™^****1^A*^^
      0     20    40    60     80    100    120    140
                        Time (min)
TMP=0,34 bar
TMP=0,60 bar
TMP=0,85 bar
TMP=1,1 bar
     UF of kiwifruit juice. Time course of permeate flux at different TMP
                         (T = 25 °C; Qf = 800 l/h)

-------
  ITM - CNR
• Istituto per la lecnolqgia delle Membrane '
         20
         15
         10
          0
            0      0.2      0.4      0.6      0.8
                                IMP (bar)
1       1.2
                  UF of kiwifruit juice. Permeate flux vs.
                                  IMP
                         (T = 25 °C; Qf = 500 l/h)

-------
  ITM - CNR
I Istituto per la Tecnologia delle Membrane '
    20
    15
    10
         X
 /l\
V
                         X
                          XX )|XX X
                  ••*   •
                              X
                        x rnoxixx >x x  xxx
                             x x>x mmoc xxx xx xx
                                                  • Qf=500 l/h
                                                  » Qf=600 l/h
                                                  * Qf=700 l/h
                                                  A Qf=800 l/h
       0
20
          40     60      80
                 Time (min)
100     120
140
     Time course of permeate flux at different axial feed flow rates
                       (TMP = 0.85bar;T=25°C)

-------
   ITM - CNR
 I Istituto per la Teciralojia delle Membrane '
                                                               T=20 °C

                                                               T=25 °C

                                                               T=30 °C
      0
20     40     60     80

              Time (min)
100
120
140
UF of kiwifruit juice. Time course of permeate flux at different temperatures
                      (TMP = 0.85 bar; Qf = 800 l/h)

-------
  ITM - CNR
I Istituto per la Teciralojia delle Membrane '
         18
     CM
         16 -
         14
         12 -
         10 -
         8
- 5
- 4
                                                                   VRF
- 2
- 1
                                                           0
           0     50    100    150    200    250     300    350

                              Time (min)
       UF of kiwifruit juice. Time course of permeate flux and VRF
     (batch concentration mode; T=25 °C; TMP = 0.85 bar; Qf = 800 l/h)

-------
  ITM - CNR
I Istituto per la Teciralojia delle Membrane '
140


120


100


 80


 60


 40


 20


  0
     0
               0.5
     1

IMP (bar)
1.5
                                                          • Before treatment of
                                                            kiwifruit juice

                                                          * After UF test and
                                                            rinsing with water

                                                          A After washing with
                                                            Ultrasil 10
           Measurement of the water flux in UF membrane module

-------
  ITM - CNR
• Istituto per la lecnolqgia delle Membrane '
  (M
   E
   o>
       0
         0        50       100      150       200      250       300

                                 Time (min)
          OD of clarified kiwifruit juice. Time course of evaporation flux

-------
  ITM - CNR
I Istituto per la Teciralojia delle Membrane '



5s
CD
o

o
CO
CO
1—




/ u
60 J
50 -

40 -



30 -
20 -

10 -
n
A
A TSSC AA
9 • [CaCI2]
0 • A
• ^

0
0
A
• A
* • .
A A «
A ^
••

U/£
- 60
- 58
- 56


- 54

- 52
- 50

- 48
/!«


~
"g
-
ss^~
^
* -^ "|
O
(0
O



        0
50
100      150
      Time (min)
200
250
300
    OD of clarified kiwifruit juice. Time course of TSS and brine concentration

-------
  ITM - CNR
• IStitUtO per la Tecm.lM.la delle Membrane '
         30
         25 -
         20 -
      V)
      o
      CO
      o
      O
      CO
      CD

      1  10
      CD
      o:
          5 -
          0
            0
50
100      150      200

      Time (min)
250
300
              OD of clarified kiwifruit juice. Time course of the viscosity

-------
 ITM - CNR
I Istituto per la Teciralojia delle Membrane '
 At low TSS evaporation flux seems to depend  mainly
 on brine concentration.  At concentration values higher
 than 40 °Brix evaporation rate depends mainly on juice
 viscosity  (viscous  polarization) and, consequently, on
 juice concentration.

-------
  ITM - CNR
I Istituto per la Teciralojia delle Membrane '
       Analytical measurements on samples coming from treatment
                    of kiwifruit juice by UF and OD

 Sample    Toted   pH Suspended Turbidity Viscosity Ascorbic  TAA*
          Soluble         Solids    (NTU)    (cSt)     add*    (rnn
          Solids         (%wfo)                   (n&lOOg) trolox)
• •
juice
m I m j
m / f^
permzate
m I m J
m / f^
retentate
CD
V^tX
retentate
12.5

12.1

13.5


65.8

3.58

3.60

3.58


3.40

5.16

0

51.5


0

299.5

0

1336.7


0

1.30

0.87

.


25.2

69.6

69.3

62.8


69.6

16.0

15.3

15.6


14.1

 : values referred to 12.5 °Bm

-------
  ITM - CNR
• Istituto per la lecnolqgia delle Membrane '
                                                       DTAA measured
                                                       D acid ascorbic
                                                         contribution to the
                                                         TAA
        20
        18
        16
        14
        12
        10
         8
         6
         4
         2
         0
             fresh       UF       UF       OD
            kiwifruit   permeate  retentate   retentate
             juice
Total antioxidant activity in samples of kiwifruit juice coming from UF and OD processes

-------
 ITM - CNR
• Istituto per la lecnolqgia delle Membrane '
       KIWI
      JUICE

    UF
PERMEATE
    OD
RETENTATE
                                                       '•

-------
  ITM - CNR
I Istituto per la Teciralojia delle Membrane '
   kiwifruit
     juice
                  pulp-
                   1
UF
                       clarified
                        juice
diluted brine

k.

~N
C(
D


3ndenser
i
            CaCL
           	       \
          evaporator  CaCL
                                                               condensate
                                                                to waste
                                                  orr
                                                 	  concentrated^
                                                               juice

 Integrated membrane process for the production of concentrated kiwifruit juice

-------
      ITM - CNR
    I Istituto per la Teciralojia delle Membrane '
>=>
                       CONCLUSIONS
The  introduction  of  membrane  technologies  in  the  industrial
transformation  cycle of the fruit juices is one of the technological
answers  to the problem  of  the production of juices  with high
quality, natural fresh taste and additive-free

The possibility  to realise integrated membrane systems in which all
the steps of the productive cycle are based on molecular membrane
separations can be considered a valid approach for  a sustainable
industrial growth within the process intensification strategy. The
aim of this strategy is to introduce in  the  productive cycles  new
technologies   characterised   by  low   encumbrance  volume,
advanced levels of automatisation capacity, modularity,  remote
control, reduced energy consumption

-------
    ITM - CNR
   I Istituto per la Teciralojia delle Membrane '
d)  The new membrane-based integrated process for the
     concentration of blood orange juice is very efficient in
     preserving the antioxidant activity of the final product
     even at high concentration (60°Bx).

El)  The blood orange concentrated  juice retains its bright
     red  colour and its  pleasant aroma,  which is on the
     contrary completely lost during  thermal concentration
     so this product is more similar to a fresh orange juice

-------
    ITM - CNR
   I Istituto per la Teciralojia delle Membrane '
    The different membrane treatments were performed on
    different pilot plants, with freezing and defreezing steps
    to preserve the juice.  So that even better results could
    be obtained on a fully integrated pilot plant

I—\ Advantages  of  the   proposed  integrated membrane
    system are  in terms of: reduction  of  clarification
    times,  simplification of the clarification  process,
    increasing of clarified juice volumes, possibility to
    operate at room temperature preserving the juices's
    freshness, aroma and nutritional value, improvement
    of the quality of the  final product and improvement
    of the productive processes

-------
     NATO CCMS/Clean Products and Processes, Italy 2003
 SLOVAK BY-PRODUCTS IN
   INTENSIFICATION OF
WASTEWATER TREATMENT
 M. VACLAYIKOYA, S. HREDZAK
     AND S. JAKA£J3KY
 SLOVAK ACADEMY OF SCIENCES
  INSTITUTE OP GEOTECHNICS
     KOSICE, SLOVAKIA

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                   NATO CCMS/Clean Products and Processes, Italy 2003
      > Significant hazards to the environment
                           *Zii»r nad Hronom
   The former Sered
   hydrometallurgical
   plant
The AI2O3 production   The coal-fired
Ziar nad Hronom       power plant EVO
                      Vojany
M. Vaclavikova etal., Slovak Academy of Sciences, Institute of Geotechnics, Kosice, Slovakia

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               NATO CCMS/Clean Products and Processes, Italy 2003
    >  Industry operations handle large volume of
      process water

    >  Heavy metals frequently occur in industrial
      effluents

    >  The solid waste dumps occupy enormous
      land areas
M. Vaclavikova et al., Slovak Academy of Sciences, Institute of Geotechnics, Kosice, Slovakia   3

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              NATO CCMS/Clean Products and Processes, Italy 2003
     RESEARCH OVERVIEW

   > Material study
     - chemical composition
     - mineral composition
     - grain size
     - magnetic susceptibility
     - pH stability

   >  Water treatment model experiments
   > Treatment experiments on real wastewater
     (not started yet)
M. Vaclavikova etal., Slovak Academy of Sciences, Institute of Geotechnics, Kosice, Slovakia

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               NATO CCMS/Clean Products and Processes, Italy 2003
      ALBANIAN LEACHING RESIDUUM
       Tab. 1:  Mineral composition
             Phase
            magnetite
             quartz
             wustite
             calcite
         ferochrompicotite
Content[%]
    54.09
    13.15
    8.02
    6.32
    5.51
M. Vaclavikova etal., Slovak Academy of Sciences, Institute of Geotechnics, Kosice, Slovakia

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                   NATO CCMS/Clean Products and Processes, Italy 2003
          Tab.  2:   Chemical composition


Element
Fetotal
Fe2+
Fe3+
Femet
Si02
AI203
CaO
MgO
Cr203
NiO
Content [%]
45.89
17.60
26.97
1.32
15.03
4.80
3.54
2.21
1.06
0.17
M. Vaclavikova etal., Slovak Academy of Sciences, Institute of Geotechnics, Kosice, Slovakia

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                   NATO CCMS/Clean Products and Processes, Italy 2003
     RED MUD FROMAL2O3 PRODUCTION
          Tab. 3: Chemical composition
\
Element
Si02
Fetotal
Fe2+
Fe3+
Ca
Mg
Al
Cr
Pb
Zn
Mn
Na
Content[%]
13.35
25.34
0.56
24.78
1.066
0.35
4.43
0.039
0.011
0.014
0.42
6.88
M. Vaclavikova etal., Slovak Academy of Sciences, Institute of Geotechnics, Kosice, Slovakia

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                NATO CCMS/Clean Products and Processes, Italy 2003
    ASH FROM COAL-FIRED POWER PLANT
     Tab. 4: Chemical/mineral composition
Chemical formula
Si02
3AI203.2Si02
Fe203
Ti02
C
Mineral
quarz
mullite
hematite
anatase
carbon
glass phase
Content [%]
4.10
2.10
8.70
0.60
18.32
62.90
M. Vaclavikova et al., Slovak Academy of Sciences, Institute of Geotechnics, Kosice, Slovakia  8

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                 NATO CCMS/Clean Products and Processes, Italy 2003
      ASH FROM COAL-FIRED POWER PLANT
       Tab. 5:   Chemical composition
Element
Fetotal
Si02
AI203
CaO
combustible matter
Content [%]
6.70
43.39
18.16
1.55
21.17
M. Vaclavikova etal., Slovak Academy of Sciences, Institute of Geotechnics, Kosice, Slovakia

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               NATO CCMS/Clean Products and Processes, Italy 2003
     WATER TREATMENT EXPERIMENTS
       Adsorption tests
       - Cadmium solutions and sorbents preparation
       - determination of optimal pH
       - batch isotherm studies
       - results evaluation
M. Vaclavikova et al., Slovak Academy of Sciences, Institute of Geotechnics, Kosice, Slovakia  10

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                NATO CCMS/Clean Products and Processes, Italy 2003
      ADSORPTION CONDITIONS

      * Sorbent concentration ....2 g.L1
      » Initial CcP+ concentration.... 20-400 mg.L1
      > Adsorption time ....24 hours (in a rotary shaker)
      » Temperature.... ambient (about 20°C)
      » InitialpH :  Albanian leaching residuum.... pH 6
                   Red mud.... pH 6
                   Magnetic fraction of ash.... pH 7
M. Vaclavikova et al., Slovak Academy of Sciences, Institute of Geotechnics, Kosice, Slovakia  11

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                   NATO CCMS/Clean Products and Processes, Italy 2003
      ADSORPTION ISOTHERM 1
        Cadmium uptake byalbanian leaching residuum
     30
     25-
     20-
   C)
   E 15
   0
   _*;
   CO
     10-
     5-
I=0.01M
pH6
        0   50  100  150  200  250   300  350
                         -1,
                 EquilC[mg.L ]
          pH6
          sorption capacity:
          27 mg.g-1
M. Vaclavikova et al., Slovak Academy of Sciences, Institute of Geotechnics, Kosice, Slovakia  12

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      60
      50-
      40-
    0)
    E 30-
    CD
      20-
      10-
                         NATO CCMS/Clean Products and Processes, Italy 2003
                   Cadmium uptake by red mud
                                           1=0.01 M
                                           pH6
                 50
100
150
200
250
300
                        EquilC [mg.L1]
                                 pH6
                                 sorption capacity:
                                 51.5 mg.g-1
M. Vaclavikova et al., Slovak Academy of Sciences, Institute of Geotechnics, Kosice, Slovakia   13

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   70-

   60-

   50-

'q> 40-

•=•30-

JS  20-
Q.
   10-

    0-

  -10
                         NATO CCMS/Clean Products and Processes, Italy 2003
            Cadmium uptake by magnetic fraction of ash
                                            1=0.01 M
                                            pH7
                  50
                       100
150
200
250
                       Equil C [mg.L1]
                                                        pH7
                                                        sorption capacity:
                                                        68.5 mg.g-1
M. Vaclavikova et al., Slovak Academy of Sciences, Institute of Geotechnics, Kosice, Slovakia  14

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                NATO CCMS/Clean Products and Processes, Italy 2003
      CONCLUSION
  >  By-products from metallurgy and power production
     were tested as sorbents in wastewater treatment
     processes

  >  Applied materials are effective sorbents for cadmium
     (probably for the other heavy metal ions too)

  >  Experiments confirmed the new possibility of by-
     products utilisation in environmental technologies

  >  By-products application in environmental technologies
     will enable the reduction of material costs with regard
     to price of commercial produced sorbents


M. Vaclavikova etal., Slovak Academy of Sciences, Institute of Geotechnics, Kosice, Slovakia  15

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    REUSED   ,
 MATERIALS FROM ZINC
INDUSTRY FOR SORPTION
 OF HYDROGEN SULFID
          Aysel T. Atimtay
 Middle East Technical University, Environmental Engineering
      Department, 06531 ANKARA, TURKEY

-------
               ntroduction
Zinc industry produces about 1.5-2 million tons of slag
per year in Turkey. This slag is rich in metal oxide
contents like FeO, ZnO, CaO, etc., however, a suitable
usage area for this slag has not been found until today.
There is a great possibility that this slag can be used in
removing H2S  from  waste gases  from  different
industrial sources. Additionally,  in  thermal power
plants  based  on  gasification  of coal  (Integrated
Gasification Combined  Cycle-IGCC),  the  coal  gas
produced contains mainly  H2S and  other  sulfurous
gases as polluting compounds.

-------
These  gases  need  to  be cleaned with  a
suitable and economical sorbent.
IGCC, >50% energy  efficiency  and about
35%  reduction  in  CO2  emission  thru
                                    ^^
increased efficiency.
The  waste  slag  from  zinc  industi
potential candidate for the removal of these
sulfiirous gases from coal gas. It is abundant
and relatively cheap.

-------
             Objectives
The objectives of this study were :
 - to study the possibility of use of waste materials
  from zinc industries in H2S clean-up, and
 - to find out the conditions  at which the best
  sorption capacity and regeneration performance
  are obtained
The study  was carried  out with the waste
materials procured from CINKUR, one L
the zinc processing plants in Turkey.

-------
           Experimental
Sulfidation of the sorbent was carried out in our
laboratory with 2-3 mm particles of zinc slag.
A gas flow rate of 92 mL/min (25°C, 1 atm) was
                                ^v
used. Reaction temperatures were 400, 500°C and
600°C.
Inlet gas composition was 0.1% H2S-10% H2 in
N2 for sulfidation experiments.
Exit H9S concentrations were measured as a
      £*
function of reaction time by a GC having a PFP]
and breakthrough curves were plotted.

-------
   Schematic diagram of the packed bed reactor-furnace
                             system
Gas
Cylinders
 H2S —
  Ha
 Air
Flow
controllers
                                                           Vent
                     Quartz Reactor
Furnace
















—




Tefl

i
                     Tubing
                   Q
              Away
              valve
                         Furnace
                         Control Unit
                                By-pass Line

-------

-------
 BET Surface Area of Fresli Sorbent
              Sorbent      BET Surface
           Particle Size,       Area  ^
               mm          (m2/g)
Zinc Slag
3.14

-------
Mercury Porosimetry Analysis of Fresh Zinc Slag
                               -3 mm
        Average pore
        diameter (|im)

        Total pore volume
        (cm3/g)

        Total Pore Area
        (m2/g)

        Bulk Density
        (g/cm3)

        Porosity
0.2403
0.6235
10.3791
 1.3116
0.3152

-------
Cumulative Pore Size Distributions of 2-3 mm Zinc Slag
0.04 -,
*B 0.035 -
| 0.03 -

h
h
[> 0.025 \
•jj 0.02 4
h-H
• 0.015 1
-(Ml 'i
^ 0.01 -
1 0.005 -
0 -
c
\

' f- * fr-f' -f ' -r f T *• T — 	 _^^__







1 10 20 30 40 50 60
Pore Diameter, \un

-------
           SEM Photographs of Zinc Slag
      '*."*£
(a) 2-3 mm (x25)    (b) 2-3 mm (x3500)   (c) 2-3 mm (x600)

-------
       XRD Analyses of 2-3 mm Zinc Slag
  700
-S
  600 -
  500 -
  -400 -
  300 -
  200 -
  100 -
    0
     o
10
                    2-3 nun Zinc Slag
20
30
40
                        2-Tetha, degree
70
so

-------

-------
    Breakthrough Curves for H2S at Different
Temperatures with 1000 ppmv Inlet Concentration
                                         400 C
                                         500 C
                                         600 C
     0
500
 1000
tune, min
1500
2000

-------
    Breakthrough Curves for H2S at Different
Temperatures with 2000 ppmv Inlet Concentration
  1.2
   1 -
  O.S -
  0.6 -
  0.4 -
  0.2 -
   0
    0
100   200   300    400   500    600   700    SOO

               time, min.

-------
                  rves for H2S with Different Inlet
Breakthrough

             Concentrations at 500°C
o
y

u
     0
                                           1000 ppmv


                                           2000 ppmv
             200
400       600


  time, min
800
1000

-------
        Sorption Capacities of Zinc Slag
              Inlet Concentrations ahd Sulfidation
                        Temperatures^
Sulfur
capacity
1000 ppmv
2000 pp
           400°    500°   600°   400°   500°   600°C
            recce     ^™
gS/lOOg   1.17    2.78    5.78    0.78   1.87   3.88
Sorbent

-------
Sulfldation Runs Using the
ixtures of Steel and Zinc Slag

-------
Weight Percentages of Waste Materials in the Sorbent
                     ^^^^^

                     Mixture
          Sorbent
Weight % out of total
                           Zinc
  Waste Mixture-1 (WM-1)
  Waste Mixture-2 (WM-2)
  Waste Mixture-3 (WM-3)

-------
  BreaktKrDugh Curves for H2S with Different Waste
       MixtureTaTSO^C and 2000 ppmv Inlet
                   Concentration
  1,2
u
   1 -
  0,3 -
  06
  0,4 -
  0,2 -
   0
     0
100
200
300
400
500
                        time, nun

-------
Sorbent Capacities of Tested Waste Mixtures at 500°C
 Sorbents
 100 % Steel-Slag
Sorbent Capacity,
g S/100 g Sorbent

       0.5 n
 WM-1
 WM-2
 WM-3
      0.75
      1.27
      2.55
 100 % Zinc-Slag

-------

-------
Breakthrough Curves for H2S After Four Successive
     Sulfidation at 500°C with 2000 ppmv Inlet
        Concentration (S=Sulfidation run)
   0
     0
100
200      300
  tune, nt in
400
500

-------
Sorbent Capacities of Zinc Slag During Cyclic Test
       Su [filiation
         number
Sorbent capacity,
g S/100 g Sorbent
                                2.67
                                1.24
                                0.96
                                1.77

-------
Breakthrough Curves for SO2 During Regeneration at
500°C with Dry Air, 350 ml/min (R=Regeneration run)
     600
      0
       0
20
40      60      SO

     time, min
100
120

-------
XRD Graph of Zinc Slag After Sulfidation at 600°C
                  with 2000 ppmv
   600
  4J
500 -

400 -

300 -

200 -

100 -

 0
      0
        10    20    30    40    50

                    2-Tetha, degrees
60
70

-------
               onclusion
Zn slag is a good candidate as a low-cost sorbent
for the removal of H2S in the temperature range of
400 - 600°C.                   ^
H2S sorption capacities increase with temperature.
The highest efficiency is achieved at 600°C and at
an inlet concentration of 1000 ppmv  H2S for the
zinc  slag.  The corresponding breakthrough times
were  1530 min. It is seen that the zinc slag can
reduce the 2000-ppmv H2S concentration down to
1-2 ppmv levels before breakthrough.

-------
Contn'd
• The  mixtures  of steel and zinc slags were also
  tested as H2S sorbents. It was seen that they gave
  good results, too. The WM-3  sorbent,  which is
  composed of 75 % zinc slag and 25 % by wt steel
  slag,  achieved   better   sorption  capacity  and
  efficiency than others including the pure zinc slag
  sorbent.
• The  regeneration results  of the sorbents showec
  that   zinc   slag   can  easily  be  regenerated.
  Appreciable amounts of  SO2 are  released during
  the regeneration of the sorbents and it can be used
  in the production of sulfuric acid.

-------
  Changes in the sulfur content of the sorbent
               Reaction Temiterature
          200°C 300°C  400°C 500°C  6<
%Sbywt.  0.36   0.51   0.65   0.83    2.47

-------
        CONCLUSIONS
In this study, availability of the metal oxide waste
materials especially the steel slag from the iron-
steel industry for the absorption of H2S was
investigated and it was  found that it is a good
candidate as a low-cost sorbent for the removal of
H2S in the temperature range of 500 - 600°1
A breakthrough time of 150 min can be reached at
a reaction temperature of 700°C.           ^^^
It was observed that iron and steel industry waste
can bring the H2S concentration down from 1000
ppmv to 1 ppmv.

-------
Conclusions Contn'd
  The XRD analysis has shown that FeS is
  formed in the particles and the sulfur
  content of the sorbent has increased about
  four folds as the temperature increased from
  400 to 600°C.

-------
   Experience with Cleaner Production in the
            Ledeko, Inc. Agricultural
   Enterprise, Letovice, The Czech Republic
           prof. Frantisek BOZEK, Ph.D.
            Military University VYSKOV
               CZECH REPUBLIC
Connection: +420 973 452 471, e-mail: bozek@feos.vvs-pv.cz

-------

-------
           JML
     Characteristics of LEDEKO, Inc.
Basic information
         Animal production
          ill
         Road transport
         Plant production
         Bakery
         Wood-processing plant
46%
25%
13%
10%
 4%
 i o/
 L 70

-------
   Determination of Priorities, Objectives and
                Choice of Indicators
The objectives:
1) cost reduction for milk production by 5 %
2) reduction of manure losses by 10 %.

The indicators:

1) reduction of costs per 1 litre of milk

2) reduction of environmental impacts that are transformed
  into economic losses and subsequently expressed in CZK.

-------
             JML
              Proposed Measures
Reconstruction of a large-scale cowshed for 450 milk cows
and removal of further 3 cowsheds.
Construction of a large-capacity dung yard and removal of
field dunghills.

-------
          Economic Benefits and Costs
         Reconstruction of a lame-scale cow-shed
            Burden in total: 17 000 000 CZK
          burden of building: 12 952 000 CZK
          burden of machine:  4 048 000 CZK
             Payback period: 8 year 93 day
        Economic effect: 4 274 550 CZK per year
Costs per 1 litre of milk: 8,30 CZK—> cost reduction for milk
                  production by 5 %
                    IRR: 10,69 %

-------
     Environmental Benefits and Costs
removal of outdated spreading of semi-liquid manure
results in smaller weed infestation of fields;
lower consumption of herbicides;
smaller number of passages;
lower soil compaction;
improvement of soil structure by means of using manure;
reduction of the consumption of industrial fertilisers and
diesel oil (by 11001), etc.

-------
             JML
                          usion
different benefits between agricultural and industry
branch by using CP
the CP strategy represents the change in the company
management

-------
NATO CCMS Pilot Study on Clean Products and Processes
  Establishing and Managing
 Waste Minimisation Clubs in
           South Africa
Susan Barclay and Chris Buckley
Pollution Research Group
University of Natal, Durban

-------
 Waste Minimisation Clubs
A group of companies working together to
reduce waste and save money
Sector-specific or cross-sectional
7 to 15 companies
Regular meetings

-------
 Pilot WMC in South Africa
2 pilot clubs formed in KwaZulu Natal
 - Metal Finishing (June 1998 to Dec 2000)
 - Hammarsdale (Nov 1998 to Dec 2000)
Sponsored by the Water Research
Commission

-------
           Results of Pilot WMC
WMC
No.       Water and
members  Effluent (kl/y)
Energy
(MWh/y)
Financial
Savings
(R/v)
Finishing
Hammarsdale 8
         1 840 000
            10800000

-------
               WMC  in  South Africa
Cape Metal Finishing
WMC for Large Industries in the Western Ca1
       :tzbur<
                                            Cape To
Cape Town
Cape Town
Set up phasf
\ugust 2000
vlovember 200'
                   2001
Gauteng Metal Finishing
Uty of Cape Town WMC
 'auteng
 ,ape To^
October 20i
 ebruary 20<
                                             -ape Town
              )ruary 2002

-------
    WMC  in  South Africa (cont.)
Cityo
WMC at the Red Cross Children's Hospitr1
City of Cape Town WMC for the Convention
WMC for the Food Industry in the Cape Metro Are
WMC for the Food and Beverage Industry in Bolan
WMC for Medium and Large Companies in Paarl
WMC for Suppliers to a Large Automotive Manufact
WMC for the Gauteng Plastics Industr-
 ity of Cape Town WMC for the Plastics Industi
 ity of Cape Town WMC for Meat Processor
City of Cape Town WMC for the Car Repair lnd>
WMC for the Wine Farms in the Breede Vail'
Cape T
Cape Towi
 :oberts
Cape Towi
  ipe Tov
 jruary 200'
irch 20i
iril 2002
ril 2002
mil 2002
 12002
it up phai
              it up pha:
              . up phase
              it up phc
              it up phar

-------
     Facilitator's Manual
Sponsored by the Water Research
Commission
Manual to provide guidence in forming and
managing a waste minimisation club in SA
Based on experiences of facilitator's of
current WMC in SA

-------
  Stages in forming a WMC
Raising awareness
Recruitment
Organisation for action
Assessments
Implementation
Analysis
Training

-------
       Funding a WMC
Free to club members
External subsidies
Company contributions

-------
            Meetings

Important aspect of a WMC
Held at least bi-monthly
Suitable venue
Site visits

-------
Barriers in Running a WMC

Lack of attendance
Lack of progress on-site
Lack of big stick
Competition between members

-------
       Internal Barriers
Lack of time
Lack of resources
Lack of finance
Lack of commitment

-------
        Success Factors
Commitment from top level
Enthusiastic project champion
Involvement of all employees
Training
Success stories
Backing from local regulators

-------
         Social Aspects
Good interaction between club members
Exchange of information and ideas
Peer pressure to succeed

-------
WMC and Local Authorities
WMC can work as a group to discuss issues
with local regulators
Metal Finishers in KZN working towards
co-regulation with eThekwini Water

-------
    Sustaining the Concept

Keeping the awareness
Publication of success stories
Support of local, provincial and national
government
Centre of information
Training

-------
            Training
Very important in promoting waste
minimisation
Trainer's and Participant's Manuals in
development stages

-------
     Acknowledgements

Water Research Commission of Southern
Africa
Club members
Club Facilitators

-------
       Network of Excellence:
Sustainable Remediation Concepts and Technologies for
    Former Industrial Sites under consideration of
   Technical -, Economical -, Legal -, Environmental -
         Socio-economical Aspects (TELES)

   abc - consultants gmbh initiative
            Viorel Harceag - ROMANIA
              Cetraro- 2003

-------
33 research organisations, companies and
universities from 14 European countries
have expressed their firm interest to
cooperate in a consortium for the
interdisciplinary development of
remediation standards for former
industrial sites in Europe
           Cetram- 2003

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The core objective : dissemination of best
practices, demonstration of projects with
integrated and outstanding approaches
on remediation strategies for former
industrial sites related to the mining-,
petrochemical-, energy-, chemical- and
heavy industry
            Cetram- 2003

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The network will access the available
know-how at the Centres of Excellence as
well as the implementation experience of the
industry, concerned with rehabilitation and
remediation of former industrial sites. An
intensive training and workshop concept will
help to overcome the existing barriers.
            Cetram- 2003

-------
The network intent to:
o bring the basic research capacities of universities and
  the applied research of consulting companies and
  production industry together.
o encourage additional and supportive research in the
  national research centres and in the existing Centres
  of Excellence and Integrated Projects.
o bridge the differences between West and East.
O doing this, TELES will develop new markets
               Cetraro-  2003

-------
The "networking" will be organised as follows:
  Coordinating Workshops
  Applied Research Activities
  Basic Research Programmes
  Public Issues/Information Group
  Cooperation Forum for non-network Partners
             Cetraro- 2003

-------
Coordinating Workshops main duties:
  Definition of the future research projects
  Selection of researchers
  Distribution of results, including the
  compilation of the so called "Remediation
  Handbook"
            Cetraro- 2003

-------
Subjects for the Applied Research Activities
© borehole technologies,
© civil engineering,
© environmental economy,
© geochemistry,
© in-situ treatment methods,
© monitoring,
© soil cover engineering,
  solid waste, water treatment met]

-------
Subjects for the Basic Research Programmes
€> acid generation,
€> best available technologies,
o bio-remediation, conceptual re-mediation,
€> geotechnics,
O hydrology,
o life cycle analysis,
© natural attenuation,
© risk assessment,
  rules / regulations / legal aspects
                 Cetram- 2003

-------
Subjects for the Public Relation Issues and
  Information Group:
  environmental policy,
  follow-up activities,
  public relation campaigning,
  socio-economic aspects
             Cetraro- 2003

-------
The Cooperation Forum for
Non-network Partners will provide
an open platform for the exchange
of technical details between the network
and non-network organisations
         Cetram- 2003

-------
  NATO/CCMS Pilot Study on Clean
	Products and Processes   ~~
       2002 Annual Meeting
           Cetrato, Italy



-------
  Topics for Cooperatio
me
         . Fet (Norway)
Cooperating Nations: USA, Turkey
Greece, Slovenia, Lithuania,
Germany, Hungary, Romania, UK^
Portugal, and Italy


-------
     Topics for Cooperatio
2. Train the trainers, imol
nt EM
    Leader:  G. Zihahy (Hungary)
    Particioatina Nations: Sloveni
    Ukraine, Lithuania





-------
   Topics for Cooperatio
             r inn
Leader:  P. Glavic (Slovenia)
                      1H1B
Ukraine, Germany, Poland, Spain
Bulgaria, Israel, Denmark, Italy,
South Africa, Turkey, Lithuania




-------
Topics for Consideration
   SltlO
Leader:  W. Zadorsky (Ukraine)
Participating Nations: Germanv
Hungary, Romania, Sweden,_
Bulgaria, Norway


-------
   Topics for Cooperatio
              ..noiogies
Leader: E. Drioli (Italy)
Participating Nations:  USA, Russia,
Israel, Portugal, Slovenia, Romania,
Denmark, Poland, Greece, Hungary,
Turkey, Spain


-------
     Topics for Cooperatio
6.  Waste minimization clubs
   Leader:  C. Buckley (S. Africa)
   Participating Nations:  Ukraine,
   Portugal, Israel, Slovenia, USA,
   Czech Republic, Bulgaria


-------
Sustainable Development Using
       Macroeconomic and
   Microeconomic Indicators
      Prof. Dr. Peter Glavic, Damjan Krajnc
            University ofMaribor,

    Department of Chemistry and Chemical Engineering,

   Smetanova 17, P.O. Box 219, SI- 2000Maribor, Slovenia

-------
Strategy of development in Slovenia
 Balanced development: economic     + +
                       social        - +
                       environmental + +
 Indicators:  GNP (p. p.) / (inhabitant)
             Index of human development
             Index of balanced sustainable development
             Index of national competitiveness
             Index of regional development

-------
               Index of balanced sustainable development
        Indicator of
         economic
        development
                    Indicator of
                       social
                   development
    Production
                     i
         Production
          structure
Elementary
indicator 1
                      I
Demography
           1
Health and
  Safety
Elementary
indicator 2
     rh
                                                          1
                        Indicator of
                       environmental
                       development
                                                           I
Environment
 resources
                         i
 Natural
resources
                       Elementary
                      indicators 154
     Total elementary indicators:  154

-------
Groups of economic indicators of
sustainable development:

  Production
  Macroeconomic stability and state consumption
  Factors of economic growth - capital
      -II-                - human resources
      -II-                - technological resources
      -II-                - natural resources
  International trade
  Consumer habits
  Structure of production

-------
Some economic indicators
Factors of economic growth
  - Technological resources:
   Computers / inh.        (%)
   Internet users / inh.     (%)
   Fraction (R&R expenditure in GDP) (%)
   Ratio export/import          (%)

-------
      Slovakia
        Poland
      Slovenia
        Greece
        Ireland
        Estonia
        Finland
      Lithuania
      Hungary
      Average
         Spain
        France
       Sweden
        Norway
      Portugal
  :ech Republic
   Great Britain
      Denmark
          Italy
       Belgium
        Austria
    Netherlands
    Switzerland
     Latvia   d
   Germany L
-O.1
                      DO.1
                      O.17
                   DO.16
                   DO.16
                 HO.14
                 DO.14
                 HO.14
                 DO.14
                O.13
              DO.12
              DO.12
              DO.12
          DO
          O.O8
          O.O8
      IO.O6
-O.O2
-O.O3
              DO.12
            O.1
.09
           O.1
            O.2
                              IO.24
                            O.22
                                       8
Changes in
standardized values
of sustainable
development
indicator for
Economy field in
years 1990 -1998
      O.3

-------
Groups of social indicators:
    Population number and structure
    Communities, migrations and regional structure
    Economical inequality
    Gender inequality
    Expected life duration
    Illnesses, bad habits and medical infrastructure
    Education
    Rights, privilege and collaboration
    Safety

-------
Some social indicators

 S 1: Population number and structure (S-I)
    • Growth (S-l)
    • Age: Over 65 years /(total population)
          Index of aging

 S 2 : Communities, migrations and regional structure
     Families:

     Migrations
     Regions:
marriages / inh.
divorces / inh.

/(urban population)
annual growth
capital population

-------













N

Great Britain
Ireland
Poland
Germany
France
Denmark
Switzerland
Hungary
Austria
Greece
Norway
Portugal
Spain
9therlands I
Finland 1
Sweden I
Czech Republic 1
Lithi
Belgiu
Slover
Estonia
Slovakia

Italy 1
-
jania I

m 1


-

-
1 Latvia





18



12

12

12

C=I1
11
CZI 1
I — I 1
0
o
-1
-1
-1
-1
-2
-3
-4
-4
-5
-5
-8
5











i n












Changes in ran
sustainable de\
indicator for S<
years 1990 - 19









-10
-5
1O

-------
Groups of environmental indicators:
  EN1:
  EN 2:
  EN 3:
  EN 4:
  ENS:
  EN 6:
  EN 7:
  ENS:
  EN 9:
Air polluting
Air pollution
Water polluting
Rivers pollution
Soil and area
Noise
Nonrenewable resources
Renewable resources
Potential resources

-------
Some environmental indicators
EN 1: Air polluting
   SO2 emissions per inh.   (kg)
   NOX emissions per inh.  (kg)
   CO2 equivalent per inh.  (kg)
EN 2: Air pollution
   SO2 mass concentration in cities  |u,g/m3
   NO mass concentration in cities  |u,g/m3

-------
      Changes in ranks of sustainable development indicator
     for Environmental field in years 1990 - 1998 for Slovenia
A
A
Wate
Pollutio
Soil and :
ir polluting
r pollution
r pollution
a of rivers
surface p.
No is e I
Nonrenewable
res ours es
1 Renewable res ours es

Average














|



|








|




-0.08
-0.03
0.02
0.07
0.12
0.17

-------
Greece
Hungary
Poland
Spain
Belgium
Lithuania
Czech Rep.
Portugal
Italy
Estonia
Latvia
Slovakia
UK
Slovenia
France
Germany
Netherlands
Ireland
Switzerland
Denmark
Austria
Finland
Sweden
Norway
0,27
"I  0,29
        Index of balanced
sustainable development
                      in 1998
      0,34
      0,37
      0,37
      0,39
      0,39
         0,44
         0,44
         0,44
           0,49
           0,50
                    0,68
                       0,74
                                  0,95

-------
     Government
 National Sustainability Assessment
  Sustainability assessment
              Linkage ?
   ^ Company 1
  Company 2
Company 3
Company Sustainability Assessment

-------
  The composite sustainable
production index - a model for
   integrated assessment of
        sustainability

-------
     A model for integration of sustainable
       production indicators into the ICSP
                Composite Sustainable Production Index
                            (/or)
Social Sub-index
Environmental Sub-index
      (7s,env)
Economic Sub-index
     (7s,econ)
  Normalized
social indicators
     Normalized
 environmental indicators
    Normalized
 economic indicators

-------
       The procedure of calculating the /rsp.
                  1. Selection of indicators
                            ^^^^m
2. Grouping of indicators (social, environmental and economic group)
      3. Judgment on indicator's impact (positive or negative)
                4. Normalization of indicators
                            ^^^^m
                  5. Weighting of indicators
               6. Calculation of sub-indices, I,
            7. Combining sub-indices into the 7CSP

-------
1. Selection of indicators

Indicators should cover main aspects of sustainable production;
 • energy and material use
 • natural environment
 • social justice and community interaction
 • economic performance
 • employees satisfaction and
 • products
 Key dimensions of indicator:
 • Unit of measurement (numbers, kilograms, EUR, hours etc.)
 • Type of measurement (total or adjusted amount)
 • Period of measurement (fiscal year, calendar year, quarter, month etc.)
 • Boundaries (product line, facility, suppliers, distributors, life cycle etc.)

-------
2. Grouping of indicators
                 Indicators of
             sustainable production
 Enironmental
   indicators
Economic
indicators
                     Social
                   indicators

-------
3. Judgment on indicator's impact
 •Aji
    increasing value has positive impact
    Example: Increased operating profit
    increasing value has negative impact
    Example: Increased air emissions per unit of production
Notation:
   Social group          j=\
   Environmental group   j = 2
   Economic group       j ' = 3
   Indicator              / = 1, .
                                .., n

-------
   4. Normalization of indicators
Uncompatibility (indicators expressed in different units)
Normalization of indicators:
                                              A,///1  ^  value of indicator
                    normalized indicator / for group
                    of indicators / for year /
Compatibility (indicators lose units)
   average value of all
   years measured
Indicator
Energy consumption (GJ/UP)
1998
4,63
1999
4,40
2000
3,77
2001
3,84
Average
4,16
       Normalized indicator for 2001:
                                           A,ijt
3,84
                                          /A,iy   4,16

-------
    5. Weighting of indicators

       The Analytic Hierarchy Process (AHP):
     N indicators  	+  (TV x TV) positive reciprocal matrix A
                                 I
                       au = 1 (i.e., on the diagonal) and
                       a.. = (\la..), ij = 1, ..., n (reciprocal property)
                                 I
                       Pair-wise comparisons
         (making independent judgments over each pair of indicators )
                                 I
dividing an indicator relative weight by the sum of relative weights in column
                                 I
                   Averaging the values across the rows
                                 i
       Normalized weight vector W containing weights (W.) of indicators

-------
Example:
Indicator
Total energy consumption £"tot
CO2 emissions *Wco2
Hazardous waste ^Vit., hazard
s
EM
^^CO2
'"wst., hazard
£"tot
1
3
4
8,00
0,12
0,38
0,50
' water
1/3
1
5
6,33
0,05
0,16
0,79
''Avst., hazard
1/4
1/5
1
1,45
0,17
0,14
0,69




Weight
0,12
0,22
0,66

-------
6. Calculation of sub-indices, /
     hjt ~
                > o
   sustainability sub-index for the group of indicatorsy in year ^
   normalized indicator / for the groupy' in year t
   weight of indicator / for the group of sustainability indicatorsy

-------
    7. Combining sub-indices into the 7CSP
   Composite sustainable production index (/CSP):
W	coefficient that represents a priori weight given to the groupy
7S Y	 sustainability sub-index for group of indicators y in year t

-------
  CASE STUDY
Sustainability Assessment of
      HENKEL

-------
          Surface
        technology
         products
           15%
Cosmetics and
   toiletries
     16%
        Laundry and
         home care
            22%
Other
          Adhesives
             23%
            Chemicals
              23%
Henkel business activities

-------
Social indicators measured by HENKEL:
Indicator
Number of occupational accidents per 200 000 hours worked
*
Number of serious occupational accidents
Number of accidents during typical production activities
Number of accidents while walking or moving around
Number of sites that received complaints from neighbors
Number of complaints from neighbors
Number of complaints due to odor
Number of complaints due to noise
Number of complaints due to dust
Number of improvement measures initiated
Number of cause already eliminated
Symbol
A^ac

^»ac, ser
^ * ac, act
^ * ac, walk
^c., sites
A^c
-< *c, odor
-< *c, noise
A^c, dust
-^Mmpr
A/elim
Unit
I/a

I/a
I/a
I/a
I/a
I/a
I/a
I/a
I/a
I/a
I/a


-------
Environmental indicators measured by HENKEL
  1. Material & Energy:
   Energy consumption
   Bought-in energy consumption per UP*
   Coal consumption per UP
   Fuel Oil consumption per UP
   Gas consumption per UP
   Water consumption per UP
   Consumption of chlorinated hydrocarbons per UP
   Production mass
                                   'UP = Unit of production (kg)

-------
2. Emissions:
   'Air emissions per UP
    CO2 emissions per UP
    NOx emissions (calculated as NO2) per UP
   » SO2 emissions per UP
   > Dust emissions per UP
    Emissions of VOC per UP
   > Wastewater per UP
   » COD emissions into surface waters per UP

-------
3. Metals & Waste:
Emissions of heavy metals into surface waters per UP
Lead, chromium, copper, nickel per UP
Zinc per UP
Waste for recycling and disposal per UP
Waste for recycling per UP
Hazardous waste for disposal per UP
Waste for disposal per UP

-------
Economic indicators measured by HENKEL:
Indicator
Sales
Operating profit
Capital expenditures
Net earnings
R&D costs
Number of employees
Symbol Unit
S
Po
IE
£N
CR
^'empl
1998
MEUR 10909
MEUR
MEUR
MEUR
MEUR
1
791
979
372
250
56291
1999
11361
857
746
404
279
56620
2000
12

1


60
779
950
359
505
320
475
2001
9410
602
664
476
255
47362
Average
11 115
800
937
439
276
55 187

-------
  Pair-comparison of environmental indicators:
Indie.  E
       tot
1 bought
'coal
F ,  F
*-ml  -i-'*
      gas
F 1
^tot "
^bought '
/Tcoal 2
M T ^\
M ^ ^^
^ water "
fWcHC '
AW 1/3
^CO2 *^
mN02 4
ms02 4
•
•
•
2 57,3
1
1
1
1
1
1/2
1
1/3
3
4
4
•
•
•
54,8
1/2
1
1
1
1
1/2
1
1/3
2
4
4
•
•
52,3
1/2
1
1
1
1
1/2
1
1/3
2
4
4
•
•
•
52,3
1/2
1
1
1
1
1/2
1
1/3
2
4
4
•
•
•
52,3
1
2
2
2
2
1
3
1
5
7
9
•
•
102,0
1
1
1
1
1
1/3
1
1/3
1
2
2
•
•
•
49,7
3
3
3
3
3
1
3
1
3
5
7
.
•
83,0
1/3
1/3
1/2
1/2
1/2
1/5
1
1/3
1
2
2
.
"
27,7
1/4
1/4
1/4
1/4
1/4
1/7
1/2
1/5
1/2
1
2
•
•
25,9
1/4 -
1/4 •
1/4 •
1/4 •
1/4 '
1/9 '
1/2 -
1/7 •
1/2 •
1/2 •
1 '
.
•
21,6
  Comparison scale: 1 (equal importance) - 9 (extreme importance of one over another)

-------
Evaluation of priority weights of
environmental indicators:
Indie.
Etot
p
'-•'bought
*^coal
EM
£gas
^ water
mcnc
'Wprod
/WCO2
WI[\O2
/HS02
Em
0,02
0,02
0,04
0,04
0,04
0,02
0,02
0,01
0,05
0,07
0,07
^-bought
0,02
0,02
0,02
0,02
0,02
0,01
0,02
0,01
0,06
0,07
0,07
£coal
0,01
0,02
0,02
0,02
0,02
0,01
0,02
0,01
0,04
0,08
0,08
E*
0,01
0,02
0,02
0,02
0,02
0,01
0,02
0,01
0,04
0,08
0,08
£gas
0,01
0,02
0,02
0,02
0,02
0,01
0,02
0,01
0,04
0,08
0,08
'water
0,01
0,02
0,02
0,02
0,02
0,01
0,03
0,01
0,05
0,07
0,09
fWCHC fWprod ^COl WINO2 ^SO2 . . \\ oiaht
1 * r V' • i_i 1 • \r
0,02
0,02
0,02
0,02
0,02
0,01
0,02
0,01
0,02
0,04
0,04
0,04
0,04
0,04
0,04
0,04
0,01
0,04
0,01
0,04
0,06
0,08
0,01
0,01
0,02
0,02
0,02
0,01
0,04
0,01
0,04
0,07
0,07
0,01
0,01
0,01
0,01
0,01
0,01
0,02
0,01
0,02
0,04
0,08
0,01 • • •
0,01 • • •
0,01 •••
0,01 •••
0,01 • • •
0,01 •••
0,02 • • •
0,01 •••
0,02 - - -
0,02 - - -
0,05 •••
0,02
0,02
0,02
0,02
0,02
0,01
0,02
0,01
0,04
0,05
0,06

-------
Normalized environmental indicators
I
1
2
3
4
5
6
7
8
9
10
11
Indicator
Total energy consumption
Symbol Weight
Etot
Bought-in energy consumption Bought
Coal consumption
Fuel Oil consumption
Gas consumption
Water consumption
Consumption of CHCs
Production mass
CO2 emissions
NO2 emissions
SO2 emissions
•
£coal
E0a
£gas
' water
^CHC
"^prod
tTl(2O2
^NO2
^SO2
•
0,02
0,02
0,02
0,02
0,02
0,01
0,02
0,01
0,04
0,05
0,06
1998
1,11
0,97
1,21
1,12
1,11
1,22
1,04
0,86
1,09
1,27
1,32
1999
1,06
1,00
1,05
1,17
1,05
1,06
1,07
0,93
1,05
1,05
1,04
•
2000
0,91
1,01
0,91
0,84
0,89
0,88
1,06
1,11
0,92
0,85
0,87
2001
0,92
1,01
0,83
0,87
0,95
0,85
0,82
1,10
0,94
0,83
0,76


-------
Sustainability sub-indices and Composite
sustainable production index:

4i
/S,2
/S,3
^CSP
1998
0,964
-0,546
-1,159
-0,611
1999
0,974
-0,309
-0,849
-0,376
2000
1,212
-0,312
-0,777
-0,286
2001
0,854
-0,273
-0,776
-0,349

-------
The variation of sub-indices and 7rsp over a period 1998-2001:
              1998
1999             2000
        Year
             2001
       Composite Sustainable Production Index
   •Economic sub-index
• Social sub-index
•Environmental sub-index

-------
  Conclusions:

  The strengths of the proposed model
• Uses normalized indicators, which enable incorporating
various indicators having different measurement units.
• Enables integration of sustainable production indicators
into sustainability sub-indices and finally into one composite
measure.
• Considers indicators according to their positive/negative
impact to overall sustainability of the company.
• Uses simple method for weighting indicators.
• Improves the quality of sustainability reporting and makes
the information more accessible to decision makers.

-------

-------
Economic Development:

   Sustainability Balance
   Competitiveness increase
   EU Membership

    Conditions:
    • Structural changes
    • Macroeconomic stability
    • Institutional reforms of transition
    Mechanisms:
    •Knowledge based society
    •Competitiveness growth
    •Effectiveness of state
    •Regionally coherent development

-------
Social Development:
  Goals:
life expectation
education and information
access to earnings
social security
social incorporation
   Similar/(GNP) as EU countries

-------
    Environmental Development:
Goals I Effective use of material resources
        Economic importance of environmental capital
        Environmental services: growth, multiplication, differentiation
        From env. protection to env. development
         24 /122 countries
         13 / 24 EU (member + candidate) countries

-------
c
C:
Swi
Netl
Germany
c
c
C
l_
Grea
1
Port i
Sp
zech Re PL
tzerland
lerlands
Austria
>lovenia
Slovakia
Ireland
•enmark
ithuania
Finland
France
Sweden
t Britain
Hungary
Estonia
Belgium
Italy
Greece
Norway
Poland
-
igal 1

>ain I
-
iblic 1


-

-

-


-
1 Latvia
_
	







1 1

I 1

I 1

I 1

I 1
-1
-1
-1
-2
-2
-2
-4
-7
2
Chai
susta
indie
field
1998
^^•5
4
4
iges in r
tillable c
:ator for
in years
•
-8
-6
-4
-2

-------
            Great Britain
                 Poland
                 No rway
                 Ireland
                 Austria
            Netherlands
                Sweden
                 France
               Germany

          Slovenia
          Slovakia

    Lithuania
    Estonia
    Latvia
-O.4
-O.2
                                        Changes in
                                        standardized values
                                        of sustainable
                                        development
                                        indicator for Social
                                        field in years 1990 -
                                        1998
O.2
O.4

-------
Czech Republic
  Great Britain
       Poland
          Italy
         Spain
       Estonia
       Norway
     Lithuania
         Latvia
       Greece
      Belgium
      Slovakia
       Austria
      Slovenia
     Germany
      Average
     Denmark
      Sweden
       France
       Finland
       Ireland
      Hungary)
      Portugalt
   Netherlands [
    I
  -O.1
                                         O.37
                  no.is
                 D 0.1
                 D O.1
               D 0.15
               1 0.15
               H O.15
                0.14
               0.14
               O.13
             ]  0.13
              O.13
        II
      I]  0.07
    U 0.06
    O.O4
-0.01
-0.01
  O.1O
O.O9
                               ] 0.29
                            0.26
                          D O.25
                         O.23
               Changes in standardized values
               of sustainable development
               indicator for Environmental
               field in years 1990 -1998
        O.1
         O.2
O.3
O.4

-------
                  eon Republic
    Switzerland
                                   Changes in ranks of
                                   sustainable development
                                   indicator for Environmental
                                   field in years 1990 -1998.
-7
-5
-3
-1

-------
Slovenian position in sustainable development
 13th place among the countries presented
 relatively balanced development
 rank 14 for economic development
 rank 13 for social development
 rank 13 for environmental development

-------
Index of balanced sustainable development in 1998
  Country
  Norway
  Sweden
  Finland
  Austria
  Denmark
  Switzerland
  Ireland
  Netherlands
  Germany
  France
  Slovakia
  UK
Index of BSD
0,95
0,85
0,74
0,68
0,57
0,50
0,49
Country
Slovenia
Estonia
Latvia
Portugal
Italy
Czech Rep.
Belgium
Lithuania
Spain
Poland
Hungary
Greece
Index of BSD
0,44
0,39
0,39
0,34
0,29
0,27

-------
"Food grade" MgCO3.3H2O - clean chemical production from waste brine

Stefka Tepavitcharova and Christo Balarew

Bulgarian Academy of Sciences, Institute of General and Inorganic Chemistry,
Acad. Georgy Bonchev Str, Bl. 11, 1113 Sofia, Bulgaria, e-mail: stepav@svr.igic.bas.bg,
Tel. (359 2) 979 39 26, Fax: (359 2) 870 50 24.
   Ecological and easy to handle technology for production of low-cost "food grade" MgCO3.3H2O
from waste sea brines after the sea salt production has been developed. The main disadvantages of
the available patents and  methods for production of MgCO3.3H2O with respect to (i)  energy
consumption; (ii) prolonged blowing through CO2;  and (iii) special equipment (ion-exchange
membranes, autoclaves) have been eliminated. This technology  leads to an improved and more
efficient management of the solar sea-salt production, to an environmental protection  of the Black
Sea coastal area as well as  meets the needs of Bulgarian market of MgCO3.3H2O as animal fodder
additive and pharmaceutic product.

   Pilot studies on the technological scheme for preparation of large "food grade" MgCO3.3H2O
crystals were carried out. MgCO3.3H2O was precipitated by mixing nondeluted waste brine from
the sea salt production with alkaline carbonate (95%  Na2CC>3  + 5% NaHCOs) during intense
stirring at 0-40°C. An important moment is the way and rate of mixing of the two solutions. Thus,
conditions of complete proceeding of crystallization in the field of MgCO3.3H2O are created, and in
this way cocrystallization of a series of carbonate double salts is avoided. The system is allowed to
recrystalize for 50 min (40°C)  to  5 h (0°C) in the presence of MgCO3.3H2O seeds under static
conditions.

   The theoretical yield of MgCO3.3H2O from 1,000 1 concentrated brine at temperatures higher
than 15 C is 180-185 kg, while  at temperatures below 15°C it is 140-160 kg. Under the conditions
of dilution, these amounts are 70-75 kg, respectively. The comparison demonstrates the advantage
of working under the optimal conditions proposed by us.

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   At present there is no Bulgarian State Standard concerning the quality and admissible admixtures
in MgCO3.3H2O permitting its application as fodder additive. The products obtained by us were
characterized on the basis of:
    •  the  admixtures  in magnesium   carbonates  admissible  according  to  the  European
       Pharmacopea standard and 10th Pharmacopea of the Soviet Union still usable;
    •  the requirements  with  respect to  phosphate content in fodder mixtures (Bulgarian State
       Standard 9775-85)
    •  Calculations  of the maximum admissible  amounts of  microelements  in fodder.  The
       calculations are made according to the requirements of the National Research Council, USA,
       concerning microadmixtures in food for different animals (sheep, cattle, pigs, poultry).
       Averaging is made having in view the universality of the product. The calculations are based
       on a maximum additive of 1% MgCOs to the food of animals, assuming that its contribution
       is maximum 10% of the total amount of food additives. The admissible additives in MgCOs
       should be equal to those in the whole ration, i.e. ten times lower. Since combined fodder
       contains 0.5% premix and the content of Mg2+ ions in the latter is 2%, the concentration of
       Mg2+ ions in combined fodder should be 0.01%. This means that the norms calculated by us
       are by almost 3 orders of magnitude lower than the needed ones.
   The all  our products meet  the Pharmacopoee  requirements  concerning As,  heavy metals,
sulphates, Fe, Cu and Ca. Mixtures of MgCO3.3H2O and NaCl with ratios varying from 1-2 % NaCl
to 3-4  fold predomination of NaCl in the mixture are used for  different kinds of animals. Taking
into account that the norm per  1 kg fodder is 0.1 g Mg2+ ions, or 0.58 g MgCO3.3H2O, the product
proposed by us leads to no increase of harmful components in the food for animals. This signifies
that both MgCO3.3H2O and its mixtures with NaCl are applicable to fodder mixtures as well as for
pharmaceutical uses.
   MgCO3.3H2O has a double  action on the body - supply  of the biogenic element Mg and decrease
of acidity in the  alimentary tract. Magnesium salts are prescribed also in the therapeutic and
prophylactic treatments of tetanic animal diseases (grazing, herbal, etc). MgCO3.3H2O  assimilation
by the animals  is high - 76%. The needs for MgCO3.3H2O in the country as additive to  animal
fodder is about 121 tons for 2005.  Combined fodders with 0.01% magnesium are used for ruminant
animals. At present, imported  MgO is used. Stored in air, however, it absorbs moisture and CO2.
MgCO3.3H2O is much cheaper than MgO and it is more stable under the fodder storage conditions
- it is stable below 80°C and dehydrates very slowly in air.

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** 
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                  OIL SPILLS
EWorld oil consumption is roughly 11.5 M m3/day

^Accidents while oil is transported have caused:

      > Ecological disasters, harmful for fish, marine
        mammals and birds

      > Extensive damage to the local economy of
        communities in coastal areas, with a strong
        effect on their income sources (fishing and
        tourism)

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       LARGEST AND  RECENT OIL SPILLS
      Date
 Ship/ Incident
          Location
 Tons
January 26,1991
JuneS, 1979
July 19,1979
August 6,1983
March 16,1978
Gulf war
IXTOCI blowout
Atlantic Empress/
Aegean Captain
Castillo de Bellver
Amoco Cadiz
Sea Island, Kuwait
Gulf of Mexico, Mexico
Caribbean Sea, off Tobago
Saldanha Bay, South Africa
Coast of Brittany, France
800 000
470 000
300 000
260 000
235 000
March 24,1989
Decembers, 1992
December 12,1999
November 19, 2002
Exxon Valdez
Aegean Sea
Erika
Prestige
Prince William Sound, Alaska, USA
La Coruha, Spain
Coast of Brittany, France
Coast of Galicia, Spain

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          THE PRESTIGE OIL SPILL
Wednesday, November 13, 2002: The single-hull oil tanker Prestige,
transporting 77,000 tons of heavy fuel oil, sent out an S.O.S. from
the Cape of Finisterre (West coast of Galicia, Spain). It was reported
that the ship was in danger of sinking because of a large crack on
the starboard side of the hull. The ship was towed to sea and the
situation deteriorated on board, due to the extremely bad weather
conditions.

Tuesday morning, November 19, 2002: The ship structure collapsed
and the tanker broke into two. It sank to 3,500 meters below sea
level, 270 km off the Spanish coast. A large quantity of oil was
released into the sea when the ship sank, with further oil spillage
observed for a considerable time after the sinking.

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                                                                   paor
         Apartirdeuru
         pruMJndid.id
         *ntr* 150 y 200m
         losc-anqu*sde Fuel
   2.000
       i
424
                  El ^PrestigeW- se parte en das
                  a las 08.00 de la manana,
                  A las 11.45, la papa empieza
                  a hundirse  y posteriarmente
                  lo hace la proa.
                               pw

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:

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          THE PRESTIGE OIL SPILL
Approximately 40,000 tons of heavy fuel oil polluted the Galician
and northern Portugal coastline. The pollution then spread to the
shores of northern Spain (Asturias, Cantabria and the Basque
Country). On December 31, 2002, it reached the French coast.
Analysis carried out identified the spilled oil as fuel oil # 6
Fuel oil # 6 is one of the so-called heavy fuel oils. It is the highest
boiling fraction of the heavy distillates from petroleum. The analysis
gave the following composition:
     > 22 % saturated hydrocarbons
     > 50 % aromatic hydrocarbons
     > 28 % resins and asphaltenes
     > Density and viscosity (15°C): 995 kg/m3 and 30,000 cst

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-.,  -
t% X -i
*• TT1"      •

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 METHODS TO CLEAN UP THE SPILL OIL
L Manual recovery
^Containment booms and barriers
^Skimmers
^>Sorbents
^Burning
^Dispersants
^Washing oil using hoses
^>Vacuum trucks
^>Shovels and road equipment

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MANUAL RECOVERY

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-------

-------
         BOOMS
Floating barriers to collect the oil

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      SKIMMERS
Skimmers are
mechanical devices
designed  to remove oil
from the water surface
  Ref.: Merv Fingas, "The Basics of Oil Spill
  Cleanup", 2nd Ed. Lewis Publishers, CRC
       Press, Boca Raton, FL (2001)
                                           Brush Drum Skimmer
                           Brush Belt Skimmer
                           UQVHG
COLLECTION WEU
                                     MOVEMENT OF VESSEL
            Adsorbent Belt Skimmer
      aOUEEZE ROLLS
           Drum Skimmer
                                                                   HQVEkEMTOF VESSEL
                                           MOVEMENT OF VESSEL
                                                 FIXED WflPER BLADES
                                                                                PUMPED
                                                                                TO STORAGE
                                                                                      COLLECTION
                                                                                        , WELL
                                       PUMPED TO STORME
                              MOVEMENT OF VESSEL  Inverted Belt Sklmmei
                                                      Diac Skimmer
                                                            Rope Skimmer

                                                         OLEOPHILIC ROPE
                                                                          ANCHORED TOIL FULLY    DIL3UCK
COLLECTION
WELL

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                       SORBENTS
 Sorbents are materials that recover oil by absorption/adsorption. They
 are used in the following ways:
  > To clean up the final traces of oil spills on water or land
  > As a backup to other containment means, i.e. sorbent booms
  > As a primary recovery means for very small spills
          Manual recovery of oil and oil-soaked sorbent
(Environment Canada. Ref.: Men/ Fingas, "The Basics of Oil Spill Cleanup", 2nd Ed. Lewis Publishers, CRC Press,
                         Boca Raton, FL (2001))

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                              SORBENTS
                      Performance of some sorbents
Typical Oil Recovery with Oil Type
(weight:weight)'
Sorbent Type
Synthetic Sorbents
polyester pads
polyethylene pads
polyolefin pom-poms
polypropylene pads
polypropylene pom-poms
polyurethane pads
Natural Organic Sorbents
bark or wood fibre
bird feathers
collagen sponge
peat moss
treated peat moss
straw
vegetable fibre
Natural Inorganic Sorbents
clay (kitty litter}
treated perlite
treated vermiculite
vermiculite
Diesel

7
25
2
6
3
20

1
1
30
2
5
2
9

3
8
3
2
Light
Crude

9
30
2
8
6
30

3
3
40
3
6
2
4

3
8
3
2
Heavy
Crude

12
35
3
10
6
40

3
3
30
4
8
3
4

3
8
4
3
Bunker
C

20
40
8
13
15
45

5
2
10
5
10
4
10

2
9
8
5
Percent
oir

90+
90+
90+
90+
90+
90+

70
80+
90+
80+
80+
70
80+

70
70
70
70
                * Recovery depends very much on the thickness of the oil, type of oil, surface type, and
                 many other factors.
                **This is the percentage of oil in the recovered product. The higher the value, the lower
                 the amount of water and thus the better the sorbent's performance.
Ref.: Merv Fingas, "The Basics of Oil Spill Cleanup", 2nd Ed. Lewis Publishers, CRC Press, Boca Raton, FL (2001)

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                     BURNING
    is technique involves controlled burning of the oil at or
  near the spill site
      major advantage is its capacity to rapidly remove large
  amounts of oil over an extensive area

^Disadvantage: toxic emissions from the large black smoke
  plume produced (PAHs, VOCs, etc.).

^> For oil to ignite on water, it must be at least 2 to 3 mm thick.
  Most oils must be contained to maintain this thickness

^Burning oil is a final, one-step solution, which requires less
  equipment and much less labour than other cleanup
  techniques

^In-situ burning can be applied in remote areas where other
  methods cannot be used because of distances and lack of
  infrastructure

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Accidental in-situ burning of
oil spill from the Aegean Sea
1992, La Coruna, Spain

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               ;DISPERSANTS

 Dispersants are chemical formulations that are applied
 directly to the spilled oil in order to remove it from the
 water surface

> Dispersants do not eliminate the problem of an oil spill
 but are intended as a means of reducing the overall
 environmental impact of an oil slick at sea and on
 sensitive foreshore environments
  il spill dispersants are composed of three main
 component groups

  > Surf ace-active agents, also known as surfactants

  > Solvents (hydrocarbon and water-based)

  > Stabilizing agents

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                DISPERSANTS (II)

^Surfactants are specifically designed chemicals that have
  both hydrophilic (water liking) and oleophilic (oil liking)
  groups in the chemical compound. These chemicals reduce
  the interfacial tension between the oil and water and helps
  the creation of small oil droplets, which move into the water
  column facilitating quicker natural biological breakdown
  (biodegradation) and dispersion
      Oleophilic      Hydrophilic
        group         group

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       HOW DO DISPERSANTS WORK?
 A dispersant agent acts in the oil spill in the following ways:
   > Reduce the interfacial tension between oil and water, breaking up the oil slick
   > Increase the volatilization rate of the lighter components of the oil
   > Decrease the surface spreading of oil on the sea
   > Increase the oxygen diffusion rate to the bulk oil phase
   > Increase of breaking frequency of the spill, avoiding that big oil spots arriving
     to the coastline
ft It* Wflf frjjm wid
   Irak; ih£ ail
    dl *cjpkti
  tnl 0f tacli
mrfscule ^dharn* -attaches fa
        wMte (he
attar aid rf ih* 'thin
fit the ail dn
 Ref.: National Oceanic and Atmospheric Association (http://response.restoration.NOAA.gov)

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        DISPERSANTS  FORMULATION

Key point: To ensure a very narrow window of physical properties, such as density,
viscosity and ignition temperature. The salinity of seawater plays an important role

"Generation" classification of oil spill dispersants:

  > First generation dispersants (1960-1970). They are no longer used in oil spill
    treatment and were "industrial cleaners", "degreasers" and "detergents" with
    high aquatic toxicity, due to their higher content of aromatic hydrocarbons

  > Second generation dispersants, specifically designed to treat oil spills at sea
    with a mixture of surfactants and solvents with much lower toxicity levels than
    the first generation ones. These dispersants were conventional low aromatic
    hydrocarbon based and applied undiluted (neat) and sprayed from vessels

  > Third generation dispersants. They are mixtures of surfactants (fatty acid
    esters, ethoxylated alcohols, amines, amides, etc.) with a concentration of 50-
    80% on partially water miscible solvents (mainly polyglycol ethers), designed to
    be applied from both aircraft and vessels as either a concentrate or diluted

"Type" classification of oil spill dispersants:

  > Type I - Conventional hydrocarbon based - used neat at sea or on foreshores.
    (2nd generation)

  > Type II - Water diluted concentrate - diluted prior to use (up to 1:10) with water.
    (3rd generation)

  > Type III - Concentrate - used neat from aircraft and vessels or on foreshores.
    (3rd generation)

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     APPLICATION  OF DISPERSANTS

Application technology includes both the transportation (boats, aircrafts,
etc.) as well as the application device (ejectors, injectors, blowers, etc.)

Aerial spraying, which is done from small and large fixed-wing aircraft as
well as from helicopters, is the most popular application method

Dispersants must be applied as  soon as possible to the thickest parts of
the oil slicks and in an optimal droplet size and rate of application. A
minimum sea energy is also required before dispersants function
effectively  - the higher the sea energy the more effective the dispersant
                                                        I •
Ref.: National Oceanic and Atmospheric Association (http://response.restoration.NOAA.gov)

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   DEGRADATION OF DISPERSED OIL
i -i uay> ~
; dispersant
- - - • - - - - - - - - - - - - - - - - - - - - - HF- .
* JL_* f U * F A C
                   •  T   *
                   *T. '
       Initial dispersion
                    Bacterial colonization
                    of disp«rsant and 	
                    dispersed ail droplet?
» -"' 1 r ,* Ji.
# ;*f'  *.   ^
  u ~ •*' £?• •>
  *,  A-
*   *        * -'»
   ->^  Bacterial degradation
     of oil and dispcrsinc
                                                         .*
                                                   of bacterial aggregates
                                                   by protozoans and
Ref.: National Oceanic and Atmospheric Association (http://response.restoration.NOAA.gov)

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                BIOREMEDIATION
Microorganisms (added or, preferably present in the environment) use the
oil as source of carbon and energy (heterotrophic microorganisms)
The consequence is that oil components are, ideally, transformed into CO2
and water
Microorganisms:
    Bacteria
    Fungi and yeasts
    Superior organisms => Phytoremediation (use trees, although
    promising not fully developed)
Metabolic routes: AEROBIC. The presence of oxygen is normally enough.
      OIL
Microorganisms
                                              CO
                                               Other organics
                               nutrients (partially oxidised, water solubi

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                  BIOREMEDIATION
Key-parameter: BIODEGRADABILITY (BDG)
^> This parameter can not be estimated for a given organic compound
^> Approximate rules to evaluate BDG:
     For a given organic family, BDG increases as molecular weight
     decreases
     For a given organic family, BDG increases as branched-character
     decreases (important in the spills of gasolines)
     As general trend the BDG decrease in this sequence:
         Alkanes>Alkenes « Alkines>Poliaromatics>Aromatics
     The presence of heteroatoms (N, S, O) increases the BDG of the
     molecule except in the case of halogens
     Polymeric materials are low degradable (i.e. resins, asphaltenes)
  As a result, the relative concentrations of the different components of the
  oil spill change as the bioremediation proceeds

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                   BIOREMEDIATION
ENVIRONMENTAL CONDITIONS

  Bioremediation has been successfully applied for shoreline cleaning (more
  than 100 km of shoreline was cleaned using this technique in Alaskian
  coast in 1989 after Exxon Valdez disaster).

  The HISTORY of the site plays an important role.  Bioremediation in dirty
  coast lines (near industries or harbours) is faster because of the presence
  of microorganisms adapted to use synthetic organic mater as substrate.

  The temperature, alkalinity (rather than pH) and salinity of the water also
  plays an important role in the degradation.  Unfortunately, these parameters
  are not easy to modify.

  The shape and density of the spill is also important. Big oil spots are
  difficult to degrade because of the hindered diffusion of oxygen to the bulk
  of the spot

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      BIOREMEDIATION:  NUTRIENTS
The presence of nutrients (specially N and P) is not enough to carry out the
bioremediation at appreciable rates

The addition of external P and/or N is needed. This aspect is a critical point
in the bioremediation since the conventional fertilizers are too soluble in
water (EUTROPHICATION)

The development of low solubility fertilizers is a crucial point in these
processes

Different methods such as salts-organic mixtures or sintering of granulates
are developed to manufacture these fertilizers

In most cases, the main task in bioremediation is the application of the
fertilizer

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BIOREMEDIATION AND EMULSIFICATION
 Biodegradation of the oil components takes place in aqueous phase

 Most of the microorganisms used in bioremediation produce different
 bioemulsifiers:
     Light emulsifiers (glycolipides and lipopeptides): efficient in reducing
     interfacial tension.

     Heavy emulsifiers (lipopolysacharides): efficient in avoiding
     recoalescence
 These bioemulsifiers are highly specific as well as biodegradable. For this
 reason, the biosynthesis of dispersants is now being developed

 In some cases (specially heavy fuels) it is necessary the addition of
 synthetic emulsifiers

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   BIOREMEDIATION vs. DISPERSION
Feature
Bioremediation     Dispersion
Rate
Destructive
Flexivility
Cost
Environment
Secondary Env. Problem
Slow
Yes
Low
Low
Mainly shoreline
Eutrophication
Fast
No
High
Medium
Mainly floating oil
Org. pollutants
                               They can be complementary!

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                            COMPARATIVE
                 Cleanup Methods for Surface Land Spills
                  Removal                   Mechanical  Enhanced
                  of Excess  Natural  Manual Oil Oil/Surface     Bio-    In-Situ Hydraulic
                     Oil    Recovery Removal   Removal  degradation Burning Measures
  Habitat
Urban         ^
Roadside      V       +        V        +
Agricultural
 land         ^       +        V        +
Grassland      V       +        V        +
Forest         ^       V        V        +
Wetland       V       V        V        x
Taiga         ^/       V        V        x
Tundra        V       V        V        x
V—acceptable or recommended
+— can be used under certain circumstances
x —should not be used
0 —only marginally acceptable
                                                                  0
V
Ref.: Merv Fingas, "The Basics of Oil Spill Cleanup", 2nd Ed. Lewis Publishers, CRC Press, Boca Raton, FL (2001)

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 LAST VISUAL AID!!
ANY SUGGESTIONS?
 ANY QUESTIONS?
   THANK YOU !!!

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             2003 NATO/CCMS Annual Meeting
          Clean Products and Processes Pilot Study
             Cetraro , Italy, May 11-15, 2003
  Cleaner Production  Policy in context of
Market Economy& Sustainable Development
 for Ukraine and other countries of transition
                    economy

                   Prof .William  Zadorsky
Ukrainian Ecological Academy of Sciences,
Ukrainian State University of Chemical Engineering
                                   ecofond@ecofond.dp.ua
                                   http://www.zadorskv.com

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  Why I proposed for collaboration the theme "CP
   policy for the transition economy countries" ?
   What is the main problems with  CP policy using in
    transition economy countries?

1.   Corruption and criminality of officials. "Criminal
    production" instead of Cleaner  Production. I write my
    last book "Ecological crimes in Ukraine"
2.   Non-controlled privatization, restructuring,
    demilitarization (with use of the most ecologically
    dangerous projects)
3.   Lack or ignoring of Sustainable Development  Concept
4.   Lack of CP legislation
5.   Lack of money

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Evolution of environmental protection (UNIDO)
  No action / lack of recognition of the problem - until
  mid-20th century
  Dispersion / "solution by dilution" (the 1960's)
  End-of-pipe treatment (the 1970's)
  Recycling  and energy recovery (the 1980's)
  Cleaner Production and preventive measures (the
  1990's)
  In future: Dematerialisation ? Industrial ecology ?
  It is (UNIDO)  for advanced countries. For transitional
  economy countries while it is "Criminal  Ecology".

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    Samples of "Criminal Ecology" in Ukraine -
          transitional economy country
Fuel with 30% of benzene (instead of limited in
civilized countries 1%). We have now New standard
on "Motor fuel" where the line "limit of benzene" is
absent.
Utilization of the rockets with "geptil" in the centre of
megapolis  Dnepropetrovsk, Pavlograd
Plant "Ista" for  lead (Pb) accumulator production in
the centre of human settlement in Dnepropetrovsk

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Cleaner Production is recognized as a tool
that can contribute to the sustainable forms
of economic development, as endorsed in
Agenda 21 adopted by the United Nations
Conference on Environment and
Development (UNCED) (Chapters 20, 30
and 34).
CP is a strategy that protects the
environment, the consumer and the worker
while improving the industrial efficiency,
profitability and competitiveness of
enterprises.

 FOR US:
CP strategy should be directed at the
industrial and agricultural development with
the "greening" of industry along with the
implementation of the concept for
adaptation and rehabilitation  of the
population and introduction of effective
systems for life support under adverse
environmental conditions.

  leaning; Indus rv
n  e t  w o r
	  .•	

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  For us CP  is possible  not as result of scientists
  experts activity but as CP 'policy' in country.

Read please the definitions (UNIDO) of "policy":


>  Everything that a Government decides to do or not to do
»  A set of interrelated decisions
»  A set of principles and directives that guide the decisions of an
  organization
>  'Policy making' is a long-term, interactive, and multi-
  stakeholder process to develop a framework to implement a
  certain policy, and to evaluate and modify its implementation
  on a regular basis.
>  Elaborating a policy document or a policy statement - such as a
  national CP Policy
>  'Policy' versus 'legislation'
>  "Pojicy" or "guidelines for actions and decisions" establish the
  setting in which an entity exists and operates .
>   "Policy" is not equivalent to "regulations" or "a legal
  framework", since they represent only one of a number of
  possible tools for policy implementation.
>  Other tools include economic incentives, information and
  education, etc.

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There is some specific for countries with  transfer  economy
policy instruments, which fall into three general categories :
   Regulatory instruments - which require or mandate specific
   behaviour, e.g. determine what is prohibited, what is allowed, and
   how to carry out certain activities

   Economic Instruments, which create incentives or disincentives for
   specific behaviours, by changing related economic conditions

   Information-based strategies , which seek to change behaviour by
   providing information. The underlying assumption is that the actors
   do not take optimal or correct decisions for lack of information or
   know-how

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    Therefore for transition economy countries CP
                    policy  requires:

Good analysis of existing sectoral policies
Inter-institutional and intersectoral effort
Strong leadership and  broad support for CP
Typical policies of relevance to CP
Industrial development policy
Environmental policy
Foreign trade policy / customs policy
Investment promotion policy
CP Fiscal policy and tax regimes
CP Energy and transport policy
CP Agricultural policy
CP Education and science and technology policy
CP Health policy

And the main - Market-based instruments

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    Samples of Market-based instruments  other
    Countries (UNIDO):

Emission fees and non-compliance fines (Mexico, Uruguay ahd
Colombia)
Grants, subsidies and financial assistance for CP (Colombia,
Subsidy for Technological Conversion in Chile)
Marketable permits (uptake of water in Chile)
Deposits and product charges (batteries and tires in Hungary,
bottles in Trinidad)
Demand-side management (Costa Rica ICE) Uruguay and
Colombia
Harmful subsidy removal (energy prices in Nicaragua)
Geern procurement guidelines (Energy Star programme in the
United States)
Argentina: reduction  of waste generation taxes for companies with
a recycling programme
Mexico: environmental taxes on gasoline depending on the lead
content
Argentina: favorable taxes to promote the use of natural gas
instead of gasoline
Lithuania: acelerated depreciation
Belgium: eco-tax on beer if the producer does not use to 95%
recycled bottles / packaging

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   Samples of Information-based strategies
Establishment of a national CP Programme  (Chile)
Waste prevention targets (US EPA's goal for 2005: reduction in per
capita municipal waste generation by 25 per cent against the 1990
level)
Public recognition and awards (CP award for industry in Nicaragua)
Product labelling (eco-labels in Chile and Uruguay for CFC-free
products)
Pollutant Release and Transfer Registers (PRTR) and public access
to environmental information (Chile, Argentina)
Public environmental reporting (Brazil)
Information clearinghouse and technical assistance (United States)
Voluntary pollution prevention agreements (Costa Rica)
Public education campaigns (energy efficiency and water savings
campaign)
Financial support for environmental measures tend to promote
'traditional' end-of-pipe control measures

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         It is necessary first of all for Ukraine and other countries of
           transition economy to realize the next program (see in
                           Abstract Booklet) :
    to accelerate adoption of the State Program for Industrial and
    Domestic Wastes Utilization with the consideration of the
    military complex potential and capacities
    to set priorities in the state poljcy of sustainable development and
    military conversion for the design and manufacturing of products related
    to the environmental protection and national use of natural resources,
    environmental monitoring and survival of the population in critical
    technogenic conditions....
•See continue in Abstract Booklet

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What is our future? How long shall we live in
country with the so-called "transitional economy"?
What type of social  and economic system will  be
formed finally  in our country? How have we to
solve our  economic,  social  and  environmental
problems?   How  can  we  ensure  sustainable
balance between the human beings, industry and
the environment? It became clear that Ukraine still
has  not adopted   the  concept  of  sustainable
development, which  today has become a basis on
the solution  of these  problems in many  other
countries.

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  Theoretical  base of every CP project
Sustainable development concept
Systematic approach
Life  cycle assessment (with logistics) and
using
What is a tools and methods of its  realization?
Unfortunately we  pay more attention to
"assessments", "accounting", "indicators" and
etc.
Soon we have to be waiting for the line of "SD
modeling" work.

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NATURE
The concept of sustainable
development includes the
following three basic
components: economic,
environmental and social.
Only the balanced progress in
all three directions, thus the
growth of economy tightly
linked with simultaneous
improvement of
environmental conditions and
solution of social problems
will promote achieving the
goals of sustainable
development.

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 I showed it one year ago. Today Aheading of
Development concept hypertrophied and  became  the
element of state policy. SD is a task of State Safety Com
       Ukraine's "Aheading of Development"
          (similar Chinese "Large Jump")
       Systematic approach
              Informatic
                                      *
   Ecology
Economy
Sociality

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Systematic approach. Life Cycle Assessment. Logistics
(for every project/object)
         Q
                                               1 - latent period
                                                2- "childhood"
                                                3 - "maturity"
                                                4 - degradation
Every period requires own methods of  CP/SD Management

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Up to now the most countries with transitional
economies have no consistent programs of
their own sustainable development. Time has
come to make transition from fruitless talks
about some peculiar paths of development of
such countries as contemporary Ukraine to
realization of concepts and methods that had
shown their efficiency in prosperous and stabile
countries.

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So, concerning the peculiar problems of Ukrair
and pther countries with transition economies
possible to recommend :
tis
To implement the concept of SD as a rule for action
on legislative, administrative and  economic levels.
To promote wide popularization of the basic ideas
ofSD.
To carry on interregional environmental and
economic policies taking into account both the
interests of the regions and those of the state as a
whole in their mutual interrelation.
The next recommendations see in Abstract Booklet

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We are not  waiting for help for this
task solving and we started
OUR CONCRETE ACTIONS.
 First of all it is creation of:
 1. Technological business-incubator
  "INTELLECTUAL SERVICE" (TBI)
 2. Pridneprovie Cleaner Production Center
  (PCPC)
 3. Innovation  and Investments Internet Market

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      TBI (first and only in Ukraine) PROVIDES foi
      innovators, scientists,  experts elaboration
      commercializing on  world market of intellectual
      production  and reception  of  investments, search of
      business partners in Ukraine and abroad, business-
      examination, consulting, audits and management on
      investments objects.

The next see in Abstract Booklet

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    TBI works under the following scheme:

1.    Preparation of information materials about development,
     organization, project (for web sites).
2.    Search of the potential partners, preparation of the offers
     on  cooperation  and  registration  of  the contractual
     attitudes.
3.    Search  together with the  partner  of  the  potential
     investors.
4.    Development together with the partner both investor of
     the business - plans and projects.
5.    Management of the project.

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Technological business-incubator
  "INTELLECTUAL SERVICE"
                        Solving of Problems Process
                                     Request to experts
                          i
       Client

                           ^^^^^^^^^^^^^^^H


                           It
          Global Network
            of Experts
       search of technologies,
         search of partners,
            search of investors
             Investments
                              Choice of
                           optimum variant
Comparison

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Technological business-incubator
  "INTELLECTUAL SERVICE"
                       Marketing Process on the new
                       technologies realization
                                     Request to experts
                                                   •advertisment
                                                   • analysis of technologies
                                                   • analysis of market
                                                   • search of partners,
                                                   • search of investors
          Investment
                             Project strategy
                         Development and design
                              management
Comparison

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   Fair Objective-
1.  investors
2. innovation c
and enterprises
3. enter
   facilit
                            contact bet\\
4.devel
                                 roject managers
                                       o
                  its on tf
        attraction of foreign funds in Ukrainiair
                    economy

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principle feature/distinction of
-air - the Fair will bring together
p»    •                • ^^   ^^
                               the
four inter-related
rkets:

-------
Our training programs (for subjects of market):
       Information technologies in the business;
       Elite education for the former high - level personnel;
       Sustainable development of enterprises and regions;
       Systematic approach and  logistic concepts as theoretical base of
       sustainable development;
       Small and Middle Enterprises (SMEs) activity  as the base of
       Restructuring and Military conversion;
        Pollution Prevention tools and methods;
       Cleaner Production concepts and SMEs activity;
       ISO 14000 on Ecological management for SMEs;
       Artificial Intellect and methods of technical creation;
       Navigation in Internet for business: search of partners, investors;
       Technological business; Transfer Technologies;
       Technological  Business Incubation;
       Life Cycle Assessment using

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   We are in realization of New
            Project:
Cleaner Technology&Energysaving
Business Incubator Internet Portal
       (www.arwsd.com)

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Interactive "warm house"
    Our task is not only to create multi-lingual information
    but also  virtual international portal. We need   more
    active   on-line functions  of our portal - expertise,
    consulting, training, audits, products and  services. It
    must be connected with  investment opportunities and
    with work within the innovative - investment  markets
    that will support SD. Therefore the Portal aims are not
    only to  be an essential platform for information, but
    also an interactive  "warm   house",  'Incubator'  for
    Sustainable  Development,  Environment and Health
    issues

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Architectural design of the Portal
  Active on-line Data base of experts, consultants,
   services and organizations,
  Data  base of transfer technologies  with  author's web-
  pages,
  Data base of on-line training courses,
  Data  base with  web  pages of investment projects, and
  also  organizations  and  persons    who  needs the
  investments,
  Date Base of investments and potential investors
  Date  Base  of  Samples  of  Regional   Programs  and
  Concepts  on Cleaner Technologies,  Energy  Saving,
  Sustainable Development, Environment and Health issues
  On-line Magazines
  On-line Shop "Goods for Surviving"

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Information Databases
   Active  on-line  Databases  of experts,   consul-ants,
   services  and organizations  Partner/member directory
   with Net Cards and presentations
   Project search and bidding system
   Knowledge Databases
   Grant offers and search
   Available SD products and services
   Regional  Programs  and Concepts  on Sustainable
   Development, Environment and Health issues

-------
Samples of concrete recent  projects:

Environmental Security: System for distant devastation of explo^
devices of all types (by A.Madatov)

-------

  It is offered a system
explosive devices of all t
grenades,cartriges for rif
 The principle of system's
 ;apsule-detonator with
      mNBHGcific radiatio
      ita^^Bfcecial ge
                 power
t devastation of
 ludirjg bombs,
 Is arid so on.
 is explosion of
 device in the whole
is radiation is
 hichlcan be mai
           s	nl
       fro i
               e genera
               »*    i •
                                         Lui

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Radiation of the generator is
modulated into pales of short
impulses, so that it isn't sensitive and
harmful for human at the density of
power which explodes detonator.
 Radiation of the generator can't be
occurred without special measurer an
protection shield against this radiation
can't be made portable. Therefore, the
system allows to discharge 100%
explosive devices that are passing
through control point without visual
control.

-------
Control points at railway stations, airports, post offices have to
be equipped with explosion-proof chambers for checking that
people, automobiles and goods can pass through.
In case of discharging of plots of land and construction (perhaps
underwater) the generator can  be located on automotive device
which is directed distantly.
Possibility of sudden getting into zone of invisible and
unnoisy action of radiating generator is a real psychological
threat for a terrorist which is brining any weapon through
control point.
In the whole, the system is able to become real means of
fighting against international terrorism.

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2. Nature protection/conservation.
Balaklava restructure project
• We have in Ukraine and other NIS very important
  problem with former military regions which are left
  by army as result of demilitarization. For sample only
  in Crimea we have about 10 such former military
  towns and cities (Balaklava, Sebastopol, Feodosia,
  Donuzlav, Ordgonikidze and etc.).

  These regions have social,
  environmental, economy
  and SD problems and
  nobody knows what it is
  necessary to do to solve its


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Balaklava (" the fish jack") is located on a
coast bent, picturesque bay. In opinion
some scientists the bay corresponds t
the description of port, where ostensibly
has got during the wanderings Odissevf
Balaklava is unique monuments of a
nature - capes Aya and Fiolent, and re
of a majestic Genoa fortress Chembal
and the rests of ancient temples cove
with poetic legends.


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  alaklava is a corner  of rare, unique beauty. Dark blue
water in a bay, ancient towers and footstep from the rocks. It
Is places, that Asleksandr  Pushkin, Valery Brusov,
Mitckeitch were singing of.

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The Ukrainian owners and businessmen
to create in Balaklava (Crimea region, Sebastopo
district), former submarine base of FSU,
international health-resort-sanitary zone (initial
name "Zone of Peace")  within the frameworks
program of regional restructuring. Preconditions for
advancement and further realization of this idea
following:
global changes in international politics;
international acknowledgement of conversion
projects, staging  by aim to change orientation of
separate peoples and world community;

-------
          uuA ' *^f

                                ••• *it v.  .      S§*IINS£
                                I -m=^,vy',58f
                                * v  .•---",;•

                                     5ff ,,-.,,
taking place native changes, in
internal politics of Ukraine and
in the relations between
countries of FSU, as their resu
submarine force was came out
from Balaklava bay and
defense enterprises stopped
work;
acknowledgement of Balaklava
by unique in all respects place,
where man must create an
international tourist zone and
use effects in science sphere,
rest, medicine;

-------
Word priority acknowledgements. Project idea of
"Zone of Peace" timely, actual and one's base is
positive, and, consequently, has a right on success;
long-term  funds enclosure in building and tourist
business is absolutely advantageous business.

-------
 On 2004 year it will be 2500 Anniversary of Balaklava. We are going to organize
 NATO ARVV not only on creation in former military city "Zone of  Peace". With
 account of it may be it will be reasonable to organize in Crimea Region NATO
 ARW  or next NATO/CCMS meeting on

"Cleaner Production  Policy in context of Market Economy&
 Sustainable Development  for transition economy countries".
 NATO symposium will has to include also restructuring problems and
 sustainable development of demilitarized  towns and cities in C9untries of
 transitional  economy are connected with cleaner production policy.

-------

-------

-------

-------
3. Communication - transfer
Ecological commercialized
      technologies

-------
    Commercialised Environmentally Friend Technologies Virtual Market
  Some commercialized technical and scientific proposals of my more 300
    patents and inventions are listed here. Mutually beneficial cooperation at
                     these projects using is possible

                 Recent Commercialised Technologies
•  Development of <                                iration processes in
   chemical engineering
•  Concurrent flow reactors for gas-liguid processes
•  Production of ultra-pure substances for the semiconductor and fibre-
   optic industries.

                             Agriculture
•  Electrosol spraying for agricultural applications
•

          Commercialized environmentally friendly technologies
•  Extension of Ecologization Concept to Cleaner Production
•
   inhabitants
•  Method and equipment for washing fine dispersion solid phase products

See continue in Abstract Booklet or in: www.: adorsky.con

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         NATO CCMS Pilot Study:
    Clean Products and Processes
                 Phase II
 Jbhas K. Sikdar (US EPA), Director
  niel Murray (US EPA), Co-Director
Prof. Enrico Drioli (Italy), Meeting Director
                                  ,

-------
Promote cooperation for improving
the common pollution landscape by
stimulating cross-national dialogues
and collaboration

Share knowledge on the methods,
tools, and technologies for making
cleaner products and processes
possible.

-------
Rational product design using life cycle assessment
Measuring pollution or wastes in processes, and
minimizing them at the enterprise level
Green chemistry and processing
Material substitution
Improving energy efficiencies
Efficient separation technologies
Sustainability and Metrics
Effective dissemination of technical knowledge

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A ii ii ii a I Meeting Activities
 Invited speakers on innovative technologies
 Topical Conference (one-day)
   Product design (Copenhagen)
   Process design (Oviedo)
   Industrial ecology (Vilnius)
   Process Intensification (Cetraro)
 Computer Cafe and Posters
 Updates on country-sponsored projects
 Tour de Table
 Visits to exemplary industrial sites

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 First meeting in Cincinnati, US (March 1998)
Second meeting in Belfast, Northern Ireland, UK
(March 1999)

Third meeting in Copenhagen, Denmark (May 2000)
Fourth meeting in Oviedo, Spain (May 2001)
Fifth meeting in Vilnius, Lithuania (May 2002)
Sixth meeting in Cetraro, Italy (May 2003)
 Initially 14 Countries,now 27 countries
 17 NATO or West European
 7 Partner Countries, Israel, Egypt & Japan

  CCMS Fellows from Portugal, Turkey

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              i
i till Pilot
3 Annual Reports (hard copies and web-based)
31 Clean Production Evaluation in member countrie
 (metal finishing, textiles, food/agricultural, etc.)
31 Portal-site on EPA website on clean
 production information
31 Journal Papers from Topical Sessions

-------
1.  Pollution Prevention Tools (USA) - On schedule and ongoing

2.  Water Conservation and Recycling in Semiconductor
   Industry: Control of Organic Contamination and
   Biofouling in Ultra Pure Water Systems
   (USA and UK) - Complete

3.  Clean Products and Processes in Textile Industry
   (USA) - Complete

4.  Clean Processes in the Turkish Textile Industry
   (Turkey) - Complete

5.  Energy Efficiency in Moldova (Moldova) - Abandoned

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6.  Cleaner Energy Production With Combined Cycle
   Systems (Turkey) - Ongoing

7.  The Danish Center for Industrial Water Management
   Update. A Case on: LCA of Alternative Scenarios for
   Water Reuse in Molded Pulp Production
   (Denmark & Turkey) - Complete

8.  International Exchange and Dissemination of Clean
   Products and Processes Information:  Within the Pilot
   Study and to Industry and the Public (USA & Germany)
   - Incomplete

9.  Fellow Projects (Portugal) - Complete

10.Use of Intelligent Systems in Pulp and  Paper Industry
   (Canada) - Abandoned

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Current Projects In the Nil
  Environmental management of industrial park by
     Israel, Turkey, Poland, Hungary, Denmark, and
     Lithuania.

  Hybrid membrane application (milk, olive oil,
     chemicals) by Spain, Russia, Italy, Poland, Denmark

  Agricultural ecology by Israel

  Sustainability indicators benchmarking by Germany,
     Norway, Hungary, Lithuania, USA

  Medical care (hospitals, diagnostic facilities that use
     radionuclides) by Czech Republic

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CQ    Denmark Technological University and Solutia
(USA),                           DTU and U.S. EPA,
DTU and Kaunas University,  Lithuania

ffl    U.S. EPA and University of Porto, Portugal

ffl    Jim Swindall (UK) guidance on University-Industry
      Cooperative Research Centers
      Denmark Technological University hosted visiting
      scientists from Turkey
      University of Oviedo, Mendeleev University in
      Moscow, and U.S. EPA

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                                r?c^n
                                U®D
Steve James (USA) for Cincinnati, '98




Prof. Jim Swindall (UK) for Belfast, '99



Prof. Henrik Wenzel (Denmark) for Copenhagen, '00



Prof. Jose Coca (Spain) for Oviedo, '01



Prof. Jurgis Staniskis (Lithuania) for Vilnius, '02
Prof. Enrico Drioli (Italy) for Cetraro, '03

-------

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Interactive Annual
• CD-ROM based
• PowerPoint and linked .pdf
 formats used
• 29 PowerPoint presentations
 (28 available as .pdf)
• Complete report (192 pages) in
 linked .pdf

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Technical Conten
• Tour de Table - 11 topics
• Pilot Project Updates - 4 topics
• University-Industry Cooperation
 - 5 topics
• Industrial Ecology Symposium -
 11 topics
• Country Annual Reports - 9
 reports

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Appendices
• Appendix A - Annual Reports
• Appendix B - Phase I Summary.
• Appendix C - Phase II Proposal
• Appendix D - List of 2002
 Annual Meeting Participants
• Appendix E - 2002 Annual
 Meeting Program
• Appendix F - Presentation Links

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2003 Annual Repor
                     //
Requirements     (g
• Submit all meeting abstracts,
 presentations, and papers by
 June 30, 2003
• Submit midterm reports by
 December 15, 2003
• 2003 Annual Report published
 by January 31, 2004

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Midterm Reports
 Update of activities related to
 clean production in delegate's
 country
 Progress on collaborative
 efforts resulting from pilot study
 Pilot project updates/reports
 Brief summaries
 Report 2-3 pages in length

-------
Pilot Study Web Sit

Portal                 ,
                       fo,
• Links to other international
 cleaner production resources
 and sites
 National web pages
  • Current delegate photo
   Web links to organization sites,
   government clean production
   resources and reports, etc.

-------
Annual Report Demo

-------
Discussion	

-------
Look to 2004
    New Pilot Projects
    Focus and Topics
   Host Country Selection
   Dates for 2004 Meeting

-------
       New Pilot Projects

Sustainability Indicators
 - Plans for 2004
New Pilot Project Proposals
Other Cooperative and Collaborative
Ventures

-------
     2004 Annual Meeting
Focus and Topic Areas
- Sustainability Indicators
- Priority industries: chemical production
  energy production; food/agriculture;
  electronics
- Balance  between product design and
  production processes
- Include service sectors

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  Selection of Host Country
Delegate Proposals
Group Discussion
Selection

-------
     2004 Meeting Dates

Other cleaner production and related
meetings
Suggestion from host delegate
Open discussion
Selection of dates

-------
      Wrap-up Discussion
Review of Recommendations for Phase II
Address sustainability issues in the Pilot

Increase dialogues among country
 delegates for ways to implement the
 individual projects

Look for funding from EU, NSF
 International and other sources

Pledge again for reporting on interim
 activities

Keep CCMS Representatives regularly
 informed
&EFA

-------