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
-------
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
-------
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
-------
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)
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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.
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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
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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).
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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.
-------
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)
-------
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
-------
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).
-------
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
-------
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
-------
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.
-------
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.
-------
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.
-------
NT \ U
'JVondhcim
Sustainability
reoortina
Socio-economic indicators
-------
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.
-------
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.
-------
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
-------
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.
-------
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
-------
\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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
Levels of EMA
Orszagos szinten
Vallalati szinten
Source: Csutora, Vallalti kornyezetvedelmi koltsegek szambavetele, III.
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
Cost Allocation
Http://hcpc.bke.hu e-mail: cleaner@enviro.bke.hu
CO
o
o
(N
Q
en
u
u
o
H
-------
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.
-------
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
-------
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
-------
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.
-------
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
-------
Cost Allocation: Step 2
Source: Csutora, Vallalti kbrnyezetvedelmi kbltsegek szambavetele, III.
-------
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)
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
r
TRACI - Applications
Process design comparisons
Life cycle impact assessments (LCIAs)
Sustainability metrics comparisons
Design for environmental assessments
Environmentally preferable products
comparisons
-------
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
-------
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
-------
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\
-------
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
-------
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)
-------
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
-------
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
-------
1st case stud
Fugitive Emissions versus
Operating Conditions:
Catalytic Reforming Process
LEPAE
IPEQ/FEUP
-------
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
-------
(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
-------
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)
-------
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
-------
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
-------
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
-------
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.
-------
•v
s
q>
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s
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
o
CM
*>
s
o
Outline
• About Process Intensification
0)
O
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
o
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
-------
•v
s
0)
o
«M
JB
o
o
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
-------
•v
s
q>
O
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10
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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
-------
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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*>
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Process Integration
• 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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• UK
• 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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10
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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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s
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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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• • PT
^^^^^^^^^^^^^^^^^^^^^^^^^^^m
^^^^^^^
^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^
^^^^^^^^^^^^^^^^^^^^^^
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
-------
£
s
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CM
*>
s
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Greece - Membrane Processes
0)
0 •- EPET (National Program):
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
-------
£
s
O
CM
Techniques:
^ micro filtration
£> I v' reverse osmosis
George Gallios, Aristotle University of Thessaloniki,
Email: gallios@chem.auth.gr
-------
£
s
0)
0 " - Govenrnment (GR):
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" "
O
George Gallios, Aristotle University of Thessaloniki,
Email: gallios@chem.auth.gr
-------
£
s
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s
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Greece - Membrane Processes
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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JB
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
-------
•v
s
q>
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i
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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
-------
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
-------
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
I
37.5
•a to
^^ ^v^
3 £
0 —
b ro
? 8
87.3
Chemicals
68.1
~&
03
n~
^
InHi
31.7
s_
CD
Q.
iotr\/
nmi ir\>
22.9
•D
0
O
?
<
t
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ryry r\
= c/;
2 o;
g Q)
c c
C 'F
Z
'
1
s?o
All other
manufacturina
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.
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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.
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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
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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
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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
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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)
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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
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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
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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
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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.
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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.
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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)
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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
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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)
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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)
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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)
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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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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.
-------
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.
-------
**
-------
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)
-------
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
-------
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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*ntr* 150 y 200m
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i
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El ^PrestigeW- se parte en das
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pw
-------
-------
-------
:
-------
-------
-------
-------
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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
-------
-------
-------
-------
-------
-------
-., -
t% X -i
*• TT1" •
-------
-------
-------
-------
-------
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
-------
MANUAL RECOVERY
-------
-------
-------
BOOMS
Floating barriers to collect the oil
-------
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
-------
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))
-------
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)
-------
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
-------
Accidental in-situ burning of
oil spill from the Aegean Sea
1992, La Coruna, Spain
-------
;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
-------
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
-------
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)
-------
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)
-------
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)
-------
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)
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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!
-------
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)
-------
LAST VISUAL AID!!
ANY SUGGESTIONS?
ANY QUESTIONS?
THANK YOU !!!
-------
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
-------
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
-------
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".
-------
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
-------
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
.•
-------
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.
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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.
-------
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.
-------
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.
-------
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
-------
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
-------
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.
-------
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
-------
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
-------
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
-------
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.
-------
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
-------
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
-------
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
-------
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
-------
We are in realization of New
Project:
Cleaner Technology&Energysaving
Business Incubator Internet Portal
(www.arwsd.com)
-------
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
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Samples of concrete recent projects:
Environmental Security: System for distant devastation of explo^
devices of all types (by A.Madatov)
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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.
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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;
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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;
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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.
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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.
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3. Communication - transfer
Ecological commercialized
technologies
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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
,
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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.
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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
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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
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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.
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Annual Report Demo
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Discussion
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Look to 2004
New Pilot Projects
Focus and Topics
Host Country Selection
Dates for 2004 Meeting
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New Pilot Projects
Sustainability Indicators
- Plans for 2004
New Pilot Project Proposals
Other Cooperative and Collaborative
Ventures
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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
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2004 Meeting Dates
Other cleaner production and related
meetings
Suggestion from host delegate
Open discussion
Selection of dates
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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
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