Proiect MANUNET ERA-NET: MNT 7-023/2010
Titlul proiectului: Introducerea catalizei si optimizarea consumului de energie in instalatii de producere a conductorilor magnetici
Acronimul proiectului: ECOWIRE


Rezumatul proiectului:
Proiectul isi propune sa realizeze o noua clasa de masini pentru fabricarea conductoriloor magnetici avand drept caracteristici principale, optimizarea consumului de energie si cataliza. Realizarea celor doua tinte implica eforturi importante in ceea ce priveste activitatea de cercetare si colaborarea intre partenerii implicati in proiect. Astfel, fabricarea conductorilor magnetici se va putea realiza in conditii ecologice, atat prin reducerea emisiilor de poluanti, cat si prin micsorarea consumului de energie electrica.
Obiectiv general:
Proiectul urmareste realizarea unei noi generatii de instalatii pentru fabricarea conductorilor magnetici izolati prin emailare care sa indeplineasca cerintele pietei privind emisii poluante mai reduse, consum mai mic de energie si productivitate mai ridicata.
Obiective specifice:
·Studiu teoretic privind reactiile chimice implicate in tehnologia de emailare
· Experimentari exploratorii pentru sinteza de noi catalizatori si caracterizarea lor
· Testare catalizatori si experimente cinetice
· Studiu termodinamic si elaborare model cinetic
· Fabricare prototip
· Experimentare prototip in instalatie industriala
Rezultate estimate:
· Introducerea de noi cuptoare pentru productia conductorilor de cupru rectangulari si a sarmelor de cupru acoperite cu fibre de sticla avand performante energetice imbunatatite, durata mare de viata si operare mai rapida
· Introducerea unui nou arzator catalitic pentru reducerea emisiei de particule mici in atmosfera
· Introducerea unui nou catalizator pentru arderea solventilor la temperature joasa. Noul catalizator va fi utilizat in instalatiile noi si pentru modernizarea instalatiilor mai vechi care functioneaza deja in intreaga lume
· Noua generatie de instalatii va permite o importanta economie de energie electrica si un impact mai mic asupra mediului pe intreaga durata de functionare a instalatieui.
Institutia coordonatoare :
NEWTECH SRL – Piedmont, Italia
Date de contact:
Coordonator Proiect: Giovanni Motta
Tel: +390321397449
E-mail: info@newtechco.191.it
Componenta Consortiului International : 
GLOSER SRL - Piedmont, Italia : Partener 2
S.C. ZECASIN S.A. – Romania : Partener 3
Autoritatea contractanta:
Centrul National de Management Programe (CNMP) – Program de finantare : “Parteneriate in domeniile prioritare”
Durata proiectului (luni): 18 (2010-2011)
Activitatile aferente partii romane (P3 - S.C. ZECASIN S.A.) in proiect:
AI.1 Studiu preliminar
AII.1 Documentare si experimentari exploratorii
AIII.1 Sinteze de catalizatori si caracterizarea lor
AIII.2 Validarea modelului experimental
AIV.1 Testarea catalizatorilor si experimente cinetice
AIV.2 Studii termochimice si elaborare model cinetic
AV.1 Realizarea prototipului
AVI.1 Experimentarea catalizatorului prototip in instalatie industriala

Bugetul proiectului (Euro):

Total

Buget

Cofinantare

1280000

679000

601000

Bugetul proiectului (lei) aferent partii romane (P3 - S.C. ZECASIN S.A.) :

Total

2010

2011

Buget

Cofinantare

Buget

Cofinantare

Buget

Cofinantare

1006200

663800

491400

474600

514800

189200

Rezultate obtinute:
Etapa I; Studiu documentar. Analiza procesului chimic
In literatura s-au raportat diferite sisteme catalitice folosite pentru combustia compusilor organici volatili (VOCs):

  1. Metale nobile (Pt, Pd) pe suport de alumina
  2. Metale nobile (Pt, Pd) pe suport zeolitic (Y, mordenite, ZSM-5)
  3. Metale nobile (Pt, Pd) pe suport mezoporos (MCM-41, SBA-15)
  4. Metale tranzitionale (Cu, Co, Cr) pe suport zeolitic (Y, mordenite, ZSM-5)
  5. Metale tranzitionale (Cu, Co, Mn) pe suport mezoporos (MCM-41, SBA-15)

Experimentarile exploratorii efectuate in etapa I s-au axat pe sinteza zeolitului ZSM-5 pentru prepararea suportului folosind Cu2+ ca faza activa. Catalizatorii Cu-ZSM-5 preparati  au fost activi in combustia catalitica in aer a urmatorilor solventi: n-heptan, n-butanol, respectiv o-xilen la temperaturi relative joase (300-500oC).
Etapa II: Experimentari preliminare pentru sinteza, caracterizarea si testarea catalizatorilor
In aceasta etapa s-au investigat materiale mezoporoase pentru prepararea sistemelor catalitice de combustie a compusilor organici volatici. Experimentarile exploratorii au inclus:

  1. Sinteza de materiale mezoporoase tip MCM-41
  2. Prepararea catalizatorilor de cupru pe support mezoporos MCM-41
  3. Utilizarea difractiei de raze X (DRX) si a masuratorilor de adsorbtie-desorbtie de azot pentru caracterizarea proprietatilor structurale si texturale ale materialelor catalitice sintetizate.
  4. Realizarea testului de combustie catalitica in aer pentru n-heptan, n-butanol, N-metilpirolidona, respectiv o-xilen. Pentru analiza produsilor de reactie s-a utilizat un analizor de gaze in combinatie cu analiza gaz-cromatografica.

Testul de combustie catalitica pentru n-heptan, n-butanol si N-metilpirolidona a aratat:

  1. Conversie ridicata in CO2 (> 90%)
  2. Urme de CO si NOx in gazele de combustie

La combustia catalitica a o-xilenului la temperatura de 400oC s-a obtinut o conversie mica (40-60%).
S-a facut o propunere preliminara pentru proiectarea noului reactor de combustie catalitica.

Etapa III. Selectarea celui mai potrivit material pentru catalizarea proceselor la diferite temperaturi


AIII.1 Sinteze de catalizatori si caracterizarea lor
Studiile experimentale s-au axat pe sinteza de materiale mezoporoase si modificarea lor cu cupru in scopul prepararii de catalizatori activi pentru combustia compusilor organici volatili (VOC). S-au preparat trei tipuri de materiale mezoporoase prin diferite cai de sinteza asistata de surfactant, astfel : MCM-41 (bromura de cetiltrimetilamoniu CTAB), SBA-15 (tribloc-copolimer Pluronic P123), respectiv HMS (dodecilamina DDA).
Analiza de difractie de raze X si adsorbtia/desorbtia N2 au evidentiat, pentru toate sintezele, formarea structurii mezoporoase avand un  inalt grad de ordonare. Sintezele cu surfactant cationic (CTAB), respectiv surfactant neionic (P123) au condus la formarea materialelor support MCM-41, respectiv SBA-15 cu structura hexagonala 2-D avand valori ale suprafetei specifice BET, de  1000-1400 m2/g si ale diametrului mediu de pori, in domeniul 2.5-6 nm. In prezenta de dodecilamina (DDA) s-a obtinut silicea mezoporoasa tip HMS caracterizata printr-o structura hexagonala 3-D cu suprafata specifica de 1200 m2/g si diametrul mediu al porilor de 2.3 nm.
Catalizatorii de cupru pe baza de materiale mezoporoase tip MCM-41, SBA-15, respectiv HMS s-au preparat prin metoda de depunere prin precipitare din solutie omogena (HDP) si extrudere.


AIII.2 Validarea modelului experimental
Caracterizarea performantelor catalitice ale catalizatorilor pe baza de materiale mezoporoase diferite, modificate cu cupru s-a facut prin reactii test de combustie a o-xilenului si n-heptanului, in conditii standard. Pe baza analizei comparative a activitatii catalitice, in corelatie cu proprietatile structurale, catalizatorul de cupru pe suport de silice mezoporoasa HMS a fost selectat ca model experimental pentru reducerea emisiilor de poluanti in instalatiile de emailare a sarmelor de cupru si aluminiu.

Etapa IV. Studiul interactiei intre gazele implicate in reactie si catalizator

A IV.1 Testarea catalizatorilor si experimente cinetice
In etapa finala a proiectului ECOWIRE, experimentarea procesului de combustie s-a facut cu amestecul de solventi cu o compozitie complexa pe baza de metoxi-alchil acetati, similara cu compozitia amestecului de solventi care se utilizeaza in instalatiile de emailare a sarmelor si benzilor de cupru si aluminiu. In studiul experimental realizat s-a explorat influenta variatiei parametrilor de reactie : temperatura, viteza spatiala orara a reactantului gazos (GHSW) si concentratia compusilor organici volatili (VOC) in aer, in conexiune cu catalizatorii de cupru pe suport mezoporos sintetizati la ZECASIN. Pe baza exterimentarilor realizate,  S-a selectat atalizatorul cu cele mai bune performante in reactia de combustie a compusilor organici pe baza de  metoxi-alchil acetati.

A IV.2 Studii termochimice si elaborare model cinetic
S-a realizat un studiu detaliat de cinetica si termodinmaica a reactiei de combustie catalitica a compusilor organici volatili.
Modelul cinetic elaborat a aratat ca reactia de combustie este o reactie de ordinul 1 in raport cu compusul organic volatil privit ca o specie individuala. Pentru fiecare reactie de combustie s-a calculat entalpia de reactie la  temperatura de 400oC. Pe baza bilantului de materiale si presupunand ca reactia de combustie a fiecarui compus organic este completa (ipoteza sustinuta de analiza gszului la iesire din reactor) s-a calculat caldura generata prin combustie si s-a evaluat cresterea adiabatica de temperatura.

A IV.3 Experimentari industriale
 Realizarea sistemului catalizator prototip – reactor catalitic
In cadrul ZECASIN s-au efectuat experimentarile de preparare a catalizatorului prototip pentru indepartarea noxelor din instalatiile de emailare. Pentru fabricarea catalizatorului prototip s-a utilizat un material suport cu structura mezoporoasa tip Al-HMS. Catalizatorul final s-a obtinut prin modificarea suportului mezoporos cu ionul Cu2+ prin precipitare omogena si extrudere in matrice de alumina. Catalizatorul prototip Cu/Al—HMS sub forma de extrudate cilindrice a avut urmatoarele caracteristici texturale : suprafata specifica BET = 450 m2/g, volumul de pori = 1.5 cm3/g si diametrul mediu al porilor = 3.14 nm.
S-a construit reactorul catalitic experimental in care s-a incarcat catalizatorul prototip diluat cu material inert pentru realizarea testelor de combustie catalitica a solventilor din instalatiile de emailare.

 Caracterizarea activitatii catalizatorului prototip
S-a determinat activitatea catalizatorului prototip in reactia de denocivizare a compusilor organici volatili in conditiile procesului de emailare. Rezultatele obtinute au evidentiat au evidentiat activitatea ridicata (conversie > 99%) a catalizatorului prototip la temperatura relativ joasa (450oC).
Testul de verificare a comportarii  catalizatorului prototip la functionarea in timp a aratat stabilitatea performantelor catalitice (valori ale conversiei in jur de 99%) la o durata de functionare de 50 de ore in reactia de combustie a amestecului de solventi pe baza de metoxi-alchil acetati, in urmatoarele conditii : temperatura = 450oC, viteza volumara = 40000 h-1 si concentratia VOC in aer = 2000 ppm.
Caderea de presiune in stratul catalitic se incadreaza in parametrii de functionare a sobei de emailare a sarmelor si benzilor de cupru si aluminiu.
Rezultatele experimentarilor efectuate la Zecasin arata ca sistemul catalizator prototip- reactor catalitic realizat in cadrul proiectului ECOWIRE ar putea  fi utilizat pentru reducerea emisiilor poluante din instalatiile de emailare. Catalizatorul pe baza de Cu/Al-HMS ar putea inlocui sistemul catalitic comercial, respectiv catalizatorul integral metalic pe baza de metale nobile.

Reactorul cu catalizatorul prototip fabricat la ZECASIN a fost instalat intr-o soba de emailare a fibrei de sticla din instalatia de productie a firmei Gebauer & Griller – Linz, Austria. S-au realizat experimentari  de testare a catalizatorului prototip, Cu/suport mezoporos Al-HMS, comparativ cu catalizatorul comercial, Pt/suport metalic. Rezultatele testelor catalitice au fost urmatoarele:

 

Catalizator comercial

Catalizator prototip

Temperatura in stratul de catalizator (oC)

480

480

Viteza de curgere a  aerului (m/s)

2

2

Concentratia VOC in gazele evacuate (mg/Nm3)

77 -105

22-37

Rezultatele testelor catalitice realizate in conditii de operare reale au aratat ca pe catalizatorul prototip  fabricat la ZECASIN s-a obtinut o reducere cu 50 – 75 % a concentratiei VOC, caderea de presiune a gazului  in stratul de catalizator  fiind in domeniul parametrilor de functionare a  instalatiei de emailare.

Link: www.zecasin.ro
Date de contact:
Directorul de proiect al partii romane (P3 – S.C. ZECASIN S.A.)
Grigore Pop
Tel: +40213163448
E-mail: office@zecasin.ro

 


MANUNET ERA-NET Project: MNT 7-023/2010

Project title: Introduction of catalysis and energy optimization in magnetic wire production plants
Project acronym: ECOWIRE
Brief description of the project:
The project aims to introduce a new class of machines for magnetic wire production, featuring energy optimization and catalysis. Both goals require a strong input from research and coordination between partners in the project. This will enable magnetic wire producers to operate in an ecologically friendly way, both reducing polluting emissions and substantially lowering electrical energy consumption
General objective:
The goal of the project is new generation of plants for the production of wires with insulating enamel, which fulfill market needs for lower pollutant emissions, lower energy consumption and higher productivity.
Specific objectives:
· Theoretical study of chemical reactions in enameling technology
· Exploratory experiments for synthesis of new catalysts and their characterization
· Catalysts testing and kinetic experiments
· Thermodynamic study and kinetic model elaboration
· Prototype manufacturing
· Prototype experiment in industrial plant
Expected results:
· Introduction of new ovens for the production of both rectangular copper wires and fiberglass covered copper wires with improved energy performances, high lifecycle and faster operation
· Introduction of a new catalytic burner to reduce small particles emission in atmosphere
· Introduction of a new catalyst to burn solvents at low temperature. The catalyst will be used both to fit new plants and to retrofit older plants already in operation worldwide
· The new generation of plants will allow an important economy of electric energy and a lower environmental impact during the entire life of the plant.
Coordinating Institution:
NEWTECH SRL – Piedmont, Italy
Contact data:
Project Coordinator: Giovanni Motta
Tel: +390321397449
E-mail: info@newtechco.191.it
International Consortium Constitution :
GLOSER SRL - Piedmont, Italy: Partner 2
S.C. ZECASIN S.A. – Romania : Partner 3
Contractant Authority: The National Centre of Programme Management (NCMP) –
“Partenership in S&T Priority Areas” funding programme
Project duration (months): 18 (2010-2011)
Responsibilities:
NEWTECH SRL and GLOSER SRL:
-  will develop the new enameling machine for copper wire with resins and fiberglass
-  will be owner of any technological advance in the architecture of the machine including the oven thermo-fluid dynamics and wire cooling system
-  will keep every right on the commercialization of the product.
S.C. ZECASIN S.A:
- will research and develop a new catalyst to be used in the polymerization oven of the new machine
- will be the main catalyst supplier for both the new production plants of NEWTWCH and GLOSER and the retro-fit of operating plants
- the new technology will be a reference to reduce pollutant emissions and ZECASIN will also benefit of royalties from patent on new catalyst.
Activities afferent Romanian part (P3 - S.C. ZECASIN S.A.) in project:
AI.1 Preliminary study
AII.1 Documentation and exploratory experiments
AIII.1 Catalysts syntheses and their characterization
AIII.2 Experimental model validation
AIV.1 Catalysts testing and kinetic experiments
AIV.2 Thermo chemical studies and kinetic model elaboration
AV.1 Prototype manufacturing

Project Budget (Euro):

Total

Budget

Own resources

1280000

679000

601000

Project Budget (lei) afferent Romanian Part (P3 - S.C. ZECASIN S.A.):

Total

2010

2011

Budget

Own resources

Budget

Own resources

Budget

Own resources

1006200

663800

491400

474600

514800

189200

Results obtained:
Stage I: Documentary study. Analysis of the chemical process
Literature reported different catalytic systems used in volatile organic compounds (VOC) combustion, namely:

  1. Alumina supported noble metals (Pt, Pd)
  2. Zeolites (Y, mordenite, ZSM-5) supported noble metals (Pt, Pd)
  3. Mesoporous materials (MCM-41, SBA-15) supported noble metals (Pt, Pd)
  4. Zeolites (Y, mordenite, ZSM-5) supported transition metals (Cu, Co, Cr)
  5. Mesoporous materials (MCM-41, SBA-15) supported transition metals (Cu, Co, Mn)

The first exploratory experiments focused on ZSM-5 zeolite synthesis to be used as support material and Cu2+ has been chosen as active phase. Cu-ZSM-5 catalysts prepared were active in catalytic combustion by air of different solvents, namely: n-heptane, n-butanol and o-xylene, respectively at relatively low temperatures (300-500oC).

Stage II: Preliminary experiments for catalysts synthesis, characterization and testing
Mesoporous materials have been investigated in this stage in order to prepare catalytic systems for VOCs combustion. Exploratory experiments included:
- Synthesis of mesoporous materials of MCM-41 type
- Preparing MCM-41 supported copper catalysts
- Using X-ray diffraction (XRD) and nitrogen adsorption-desorption      measurements to characterize structural and textural properties of catalytic    materials synthesized.
- Performing catalytic combustion test with different volatile organic compounds:            n-heptane, n-butanol, N-methylpyrolidone and o-xylene, respectively. A gas       analyzer in combination with gas chromatographic analysis was used for reaction       products analysis.
Catalytic combustion test of n-heptane, n-butanol and N-methylpyrolidone, respectively showed:
- The high conversion   (> 90%) in CO2
- The presence of CO and NOx as traces in exhausted gases
A lower conversion (40-60%) at the temperature of 400oC has been obtained for the catalytic combustion of o-xylene.
A preliminary proposal has been made for the design of the new catalytic combustion reactor.

Stage III. Selection of the most suitable material to catalyze processes at different temperatures


AIII.1 Catalysts syntheses and their characterization
Experimental studies have been focused on mesoporous    combustion reaction. Three types of mesoporous materials have been prepared by different surfactant assisted synthesis routes, namely: MCM-41 (cetyltrimethylammonium bromide CTAB), SBA-15 (triblock-copolymer Pluronic P123) and HMS (dodecylamine DDA), respectively.
X-ray diffraction and N2 adsorption/desorption measurements evidenced that highly order mesoporous structures have been obtained for all syntheses. Support materials of 2-D hexagonal structure of MCM-41 and SBA-15 type have been prepared by using cationic surfactant (CTAB) and non ionic (P123) surfactant, respectively. The following textural properties have been obtained: BET specific surface areas of 1000-1400 m2/g and average pore diameters of 2.5 - 6, respectively. Neutral surfactant (DDA) assisted synthesis led to the 3-D hexagonal structure of HMS type mesoporous silica having a BET surface area of 1200 m2/g and an average pore diameter of 2.3 nm.
Mesoporous materials of MCM-41, SBA-15 and HMS type based copper catalysts have been prepared by homogeneous-deposition precipitation (HDP) method followed by extrusion.


AIII.2 Validation of the experimental model
Standard test reactions of o-xylene and n-heptane combustion have been used to characterize the catalytic performances of the different mesoporous materials supported copper catalysts. Based on the comparative analysis of the catalytic activity, in connection with structural properties, HMS mesoporous silica supported copper catalyst has been selected as the experimental model to reduce pollutant emissions in the copper and aluminum wires enameling plants

Stage IV. Study of the interaction between the gases taking part in the reaction and catalyst
A IV. 1 Catalysts testing and kinetic experiments
The final stage of the ECOWIRE project included catalytic combustion experiments with methoxy-alkyl acetates based solvents mixture used in copper and aluminum wires enameling plants. The following parameters have been explored in the experimental study: temperature, gaseous hourly velocity space (GHSV) and VOC concentration in air in connection with the composition of copper supported mesoporous materials developed at ZECASIN. The selected catalyst has been taken into account to prepare a large quantity of catalyst to be used in enameling plant.

A IV. 2 Thermo chemical studies and kinetic model elaboration
A statistical model (the 2nd degree polynomial) was derived to examine and predict the behavior of the system in the range of studied parameters. The statistical model fitted well the experimental data. A kinetic model developed indicated that the combustion is a first order reaction in report to the volatile organic compound (VOC) regarded as a single species.
Calculations were made to obtain relevant thermodynamic properties of the VOC involved in the studied reaction system. Using the data in the material balance and assuming that the combustion is complete for each VOC considered (according to the chemical analysis of the exit gas), the heat generated by the combustion was computed and the adiabatic temperature rise has been calculated.

A IV.3 Industrial experiments
Performing prototype catalyst-catalytic reactor system
Experimental runs to manufacture the prototype catalyst to burn volatile organic compounds containing emissions in enameling plants have been performed. The mesoporous Al-HMS has been used as a support material in prototype catalyst manufacturing and copper was the catalytic active component. The copper containing Al-HMS has been prepared by homogeneous deposition - precipitation procedure. The prototype catalyst has been obtained by extrusion using alumina as a binder. The prototype catalyst had the following textural characteristics: BET surface area = 450 m2/g, pore volume = 1.5 cm3/g and average pore diameter = 3.14 nm.

Characterization of the prototype catalytic activity in volatile organic compounds combustion reactions according to enameling process conditions
Detailed investigations of the Cu/Al-HMS catalyst activity as well as time stability test in the combustion of methoxy-alkyl acetates solvents mixture were performed. The high activity of Cu/Al-HMS catalyst (conversion > 99%) evidenced at a temperature of 450oC and GHSV of 40000 h-1.
Catalyst life test demonstrated that a good stability of the catalytic activity has been obtained for a lifetime of 50 h in the following conditions: temperature of 450oC, GHSV of 40000 h-1 and VOC concentration in air of 2000 ppm.
The drop pressure of the gas flow in the catalytic bed had a value of 4 mm H2O, which is situated in the running parameters range of the enameling oven.
The experimental data show that a new prototype catalyst – catalytic reactor system has been developed in ECOWIRE project, which is suitable to be used in pollutant concentration reducing in enameling plants. The new Cu/Al-HMS based catalyst could be used to replace the current commercial noble metal based all metallic catalyst.

The prototype catalyst containing reactor manufactured at ZECASIN has been installed into a fiberglass enameling machine in the production plant at Gebauer & Griller in Linz, Austria. Comparative testing runs in real operating conditions have been carried out with current commercial catalyst, Pt/metallic support and prototype catalyst, Cu/ Al-HMS mesoporous support, respectively.
The following testing results have been obtained:

 

Commercial
catalyst

Prototype
catalyst

Catalytic bed temperature (oC)

480

480

Air flow speed (m/s)

2

2

VOC pollutant concentration in exhaust gases (mg/Nm3)

77 -105

22-37

The testing results showed that a lower VOC pollutant concentration by 50 -75 % in gas emissions with no increase in the pressure drop of the gas flow passing through the catalyst bed has been obtained using the prototype catalyst manufactured at ZECASIN.

Link: www.zecasin.ro
Contact data:
Project Director of the Romanian Part (P3 – S.C. ZECASIN S.A)
Grigore Pop
Tel: +40213163448
E-mail: office@zecasin.ro





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