General assessment of the catalytic production of hydrogen from renewable oxygenates: catalysts preparation and characterization; evaluation of ethanol and glycerol steam reforming processes for hydrogen production in terms of thermodynamic aspects, conceptual layout; optimization of bioethanol preparation method from wood waste; possibilities of energetic valorization of glycerol.
CO, P1, P2, P3
1
8
2
Hydrogen production by catalytic steam reforming of bioethanol obtained from wood waste: raw bioethanol physico-chemical characterization, catalysts activity and selectivity for raw ethanol SR; modeling and simulation of the process, model validation.
CO, P1, P2
9
18
3
Technological parameters for hydrogen production by catalytic steam reforming of waste glycerol solutions resulted in biofuels production: characterization and partial purification of waste glycerol solutions, catalytic and reaction parameters for H2 production by waste glycerol SR; modeling and simulation of the process, model validation; design and realization of laboratory scale experimental set-up.
CO, P1, P2, P3, P4
19
32
4
Laboratory scale catalytic technology and experimental set-up for hydrogen production by steam reforming of hydroxylic compounds obtained as biomass processing wastes; techno-economic and environmental impact evaluations, dissemination activities (patent application, articles etc.)
CO, P1, P2, P3, P4
33
36
5
Consortium management activities
CO
1
36
Table 2: Phase description (for each Phase-max 2 pages)
Phase no.
1
Phase title
General assessment of the catalytic production of hydrogen from renewable oxygenates: catalysts preparation and characterization; evaluation of ethanol and glycerol steam reforming processes for hydrogen production in terms of thermodynamic aspects, conceptual layout; optimization of bioethanol preparation method from wood waste; possibilities of energetic valorization of glycerol.
Involved partners
CO
INCDTIM
P1
UBB
P2
ICIA
P3
Reviva
Total
Person-months
30
12
16
2
60
Start month
1
End month
8
Objectives
O1.1 The preparation and characterization of new catalysts of type Me-Ni/oxide1-oxide2.
O1.2 Evaluation of ethanol and glycerol steam reforming processes and conceptual layout;
O1.3 Optimization of bioethanol obtaining method from wood waste;
O1.4 Study of the possible energetic valorization of biomass wastes.
Description of work (possibily broken down into tasks) and role of participants
Task I – related to O1.1 and performed by CO
A1.1 The preparation of mixed catalysts based on alumina and zirconia supported Ni (6-10 wt.%) and additivated either with noble metals (Au, Ag, Pt, Rh) or with rare earth oxide (La2O3, CeO2, Y2O3). The concentration of additional metal is less or maximum 1 wt.% and of additional oxide is less or maximum 6%. The catalysts will be prepared by classic impregnation and/or by sol-gel methods.
A1.2 Structural characterization of the prepared gold catalysts using the following modern techniques: X-Ray Diffraction (XRD) – determination of metal crystallites sites, determination of oxide crystallinity, H2 chemisorption – estimation of catalytic active surface area; N2 adsorption desorption isotherms – determination of total surface area and porosity; Transmission Electron Microscopy (TEM-EDX) – determination of metal nanoparticles size and distribution; Thermo Programmed Reduction (TPR) – determination of metal reducibility on the surface, estimation of type and nature of catalytic active sites, H/D isotopic exchange – determination of number of surface OH groups.
Task II – related to O1.2 and performed by P1 (UBB)
A 1.3 Evaluation by thermodinamic modeling and simulation the ethanol and glycerol steam reforming processes in term of process conditions e.g. temperature, pressure and catalysts influence on conversion rates, resulted products etc.
A 1.4 Conceptual layout of ethanol and glycerol steam reforming processes for hydrogen production (this activity implies the collaboration of P1 with CO, P2 and P3).
Task III – related to O1.3 and performed by P2 (ICIA)
A 1.5 Developing the method of bioethanol production from wood waste and improving process parameters. Experimenting with various types of hydrolysis (acid and enzymatic) for fermentable sugars. Analysis of intermediary compounds will be done.
A 1.6 Experimenting in order to improve the existing method for bioethanol production: increasing of fermentable yield, eliminating of the inhibitors, temperature of fermentation, time of fermentation, pH, concentration of inoculum and nutrients.
Task IV - related to O1.4 and performed by P3 (Reviva)
A 1.7 Energetic evaluation of biomass wastes.
A 1.8 Study of possible usage of glycerol wastes in energetic purpose.
Deliverables (brief description and month of delivery)
D1.1 Preparation method for mixed catalysts – 3rd month
D1.2 Alumina supported Ni based mixed catalysts samples complete characterized from morphological and structural point of view – 8th month
D1.3 Report for evaluation of ethanol and glycerol steam reforming processes for hydrogen production and conceptual layout – 8th month
D1.4 Optimized method for bioethanol production from wood waste – 8th month
D1.5 Report of energetic valorization of biomass wastes – 8th month
Phase no.
2
Phase title
Hydrogen production by catalytic steam reforming of bioethanol obtained from wood waste: raw bioethanol physico-chemical characterization, catalysts activity and selectivity for raw ethanol steam reforming; modeling and simulation of the process, model validation.
Involved partners
CO
INCDTIM
P1
UBB
P2
ICIA
Total
Person-months
30
15
30
75
Start month
9
End month
18
Objectives
O2.1 Bioethanol preparation and physico-chemical characterization.
O2.2 Establishing the technological parameters, catalytic system and reaction conditions for hydrogen production by bioethanol steam reforming.
O2.3 Modeling and simulation of bioethanol steam reforming process, model validation, process integration aspects, energy consumptions.
Description of work (possibily broken down into tasks) and role of participants
Task I – related to O2.1 and performed by P2 (ICIA)
A 2.1 Obtaining of fermentation medium and bioethanol as raw material for biohydrogen production.
A 2.2 Physico-chemical characterization of fermentation medium and bioethanol.
The composition of fermentation medium (content of secondary alcohols, acids, furfural, HMF) and composition of obtained ethanol (ethanol – water ratio, alchohol concentration, esters content) will be estabilished.
Task II – related to O2.2 and performed by CO
A 2.3 The Ni based catalysts prepared and characterized in the previous phase are tested in ethanol steam reforming at atmospheric pressure and temperatures ranging from 200 to 400°C. The ethanol – water ratio will be correlated with the information received from P2 to better mimic the bioethanol composition obtained from wood waste.
A 2.4 The following parameters will be established for each catalyst and reaction conditions: ethanol conversion, H2 selectivity, H2 production, catalyst deactivation (decrease of ethanol conversion with time on stream).
A 2.5 In parallel with A2.4, the catalysts with promising results in H2 production by synthetic ethanol-water mixture reformation will be tested for hydrogen production by catalytic steam reforming of crude bioethanol obtained from wood waste. Altenativelly the ethanol solution can be diluted to reach the point with optimum maximum conversion – minimum coke deposition. The catalalytic process with the optimum balance between ethanol conversion, hydrogen production and catalyst stability will be used for further technological assays. Experimental data will be provided to P1 for model validation.
Task III – related to O2.3 and performed by P1 (UBB)
A 2.6 Mathematical modeling and simulation of bioethanol steam reforming process using dedicated process flow modeling software packages (e.g. ChemCAD, Aspen Plus etc.).
A 2.7 Model validation using experimental data, interpretation of simulation results. Evaluation of process integration issues (mass and energy), utilities and energy consumptions.
Deliverables (brief description and month of delivery)
D2.1 Bioethanol obtained and characterized – starting with 11th month
D2.2 Report of evaluation by modeling and simulation of bioethanol steam reforming processes for hydrogen production – 18th month
D2.3 Technological parameters for laboratory scale H2 production by steam reforming of crude bioethanol obtained from wood waste – 18th month
D2.4 2 papers in international recognized journals (ISI ranked) – 18th month
D2.5 3 presentations at an international scientific meeting – up to the 18th month
Phase no.
3
Phase title
Technological parameters for hydrogen production by catalytic steam reforming of waste glycerol solutions resulted in biofuels production: characterization and partial purification of waste glycerol solutions, catalytic and reaction parameters for H2 production by waste glycerol SR; modeling and simulation of the process, model validation; design and realization of laboratory scale experimental set-up.
Involved partners
CO
INCDTIM
P1
UBB
P2
ICIA
P3
Reviva
P4
Rokura
Total
Person-months
40
20
24
10
34
128
Start month
19
End month
32
Objectives
O3.1 Physico-chemical characterization and possibility of partial purification of waste glycerol solutions from bio-diesel production using original BIOVALP technology.
O3.2 Establishing the optimum technological parameters (raw material composition, catalysts performances and stability, reaction conditions) for laboratory scale H2 production by waste glycerol solutions steam reforming.
O3.3 Modeling and simulation of glycerol steam reforming process, model validation, process integration aspects, utilities and energy consumptions.
O3.4 Design and realization of laboratory scale experimental set-up.
Description of work (possibily broken down into tasks) and role of participants
Task 1 – related to O3.1 and performed in collaboration by P2 and P3
A 3.1 Development of original BIOVALP technology in order to obtain wastes (washing waters) with higher concentration of glycerol.
A 3.2 Determination of chemical composition of residual washing waters resulted in biodiesel fabrication.
A 3.3 Identification and quantitative determination of compounds with possible poisoning effect on steam reforming catalysts (activity performed in collaboration with CO).
A 3.4 The extraction of catalysts dangerous compounds from waste glycerol solutions. A purification method will be provided.
Task 2 – related to O3.2 and performed by CO
A 3.5 Establishing the experimental conditions and the reaction products analyzing conditions for glycerol steam reforming at atmospheric pressure and temperatures ranging from 500 to 700°C using 1g of noble metal and/or rare earth oxide promoted Ni catalysts. The catalytic set-up will be configured to permit the catalytic reaction and on-line analysis of both, gaseous and liquid fractions of the reaction products; an analytical method will be provided.
A 3.6 Establishing the catalytic parameters. The following parameters will be determined for each catalyst: glycerol conversion, composition of reaction products mixture, H2 selectivity, H2 production, catalyst deactivation and characterization of deposited coke (in order to better describe the catalyst deactivation process). The following methods will be used for characterization of deposited carbon: Thermogravimetry (TGA), Thermo Programmed Oxidation (TPO), Electron Microscopy (TEM). A correlation between the type and amount of deposited coke, catalyst nature and reaction conditions will lead to improvement of catalyst lifetime with direct consequences in economic efficiency of the hydrogen production.
A 3.7 The catalytic system with best performances found in A 3.4 is tested in catalytic steam reforming of crude glycerol partial purified provided by P4. The best conditions for hydrogen production will be established. A special attention will be paid to the determination of catalysts deactivation mechanisms in order to improve the catalyst lifetime. If the hydrogen production is much lower comparing with results obtained in A 3.6 further purification or changing of catalytic system will be performed.
A 3.8 Design, production and experimentation of hydrogen separator based on Pd membrane.
Task 3 – related to O3.3 and performed by P1 (UBB)
A 3.9 Mathematical modeling and simulation of glycerol steam reforming process using dedicated process flow modelling software packages (e.g. ChemCAD, Aspen Plus etc.),
A 3.10 Model validation using experimental data, interpretation of simulation results. Evaluation of process integration issues (mass and energy), utilities and energy consumption.
Task 4 – related to O3.4 and performed by P4 (Rokura) and CO (INCDTIM)
A 3.11 Design the experimental set-up for using of 10 g of catalysts in glycerol steam reforming at atmospheric pressure and temperatures ranging from 500 to 700°C catalyzed by noble metal and/or rare earth oxide promoted Ni catalysts.
A 3.12 Building the experimental set-up composed by: evaporator, catalytic reactor and hydrogen separator.
A 3.13 Experiment the laboratory scale catalytic technology for hydrogen production by steam reforming of waste glycerol.
Deliverables (brief description and month of delivery)
D3.2 Report of evaluation by modeling and simulation of glycerol steam reforming processes for hydrogen production – 32nd month
D3.3 Technological parameters for laboratory scale H2 production by steam reforming of waste glycerol solutions from biodiesel fabrication – 32nd month
D3.4 Experimental set-up for hydrogen production from waste glycerol solutions
D3.5 2 papers in international recognized journals (ISI ranked) – 32nd month
D3.6 2 presentations at an international scientific meeting – up to the 32nd month
Phase no.
4
Phase title
Laboratory scale catalytic technology and experimental set-up for hydrogen production by steam reforming of hydroxylic compounds obtained as biomass processing wastes; techno-economic and environmental impact evaluations, dissemination activities (patent application, articles etc.)
Involved partners
CO
INCDTIM
P1
UBB
P2
ICIA
P3
Reviva
P4
Rokura
Total
Person-months
12
6
12
3
12
45
Start month
33
End month
36
Objectives
O 4.1 Presentation of laboratory scale technology for hydrogen production from hydroxylic compounds obtained as biomass processing wastes by steam reforming.
O 4.2 Dissemination activities, intellectual property rights, future development
Description of work (possibily broken down into tasks) and role of participants
The activities of this phase are related to one major task: presentation of the proposed laboratory scale technology with techno-economical, environmental and scale-up analyses. These activities imply the colaboration of all parteners.
A 4.1 Development of laboratory scale technology for hydrogen production from waste glycerol solutions resulted in biodiesel fabrication.
A 4.2 Techno-economical and environmental assessment of hydrogen production from hydroxylic compounds obtained as biomass processing wastes by steam reforming.
A 4.3 Scale-up analysis of the proposed technology.
A 4.4 Potential implementation of developed technology.
A 4.5 Intelectual property aspects (patent application), dissemination of project results (articles, conference comunications).
Deliverables (brief description and month of delivery)
D4.1 Laboratory scale technology for hydrogen production from waste glycerol solutions resulted in biodiesel fabrication – 36th month
D4.2 Techno-economic and environmental impact evaluations of hydrogen production by hydroxylic compounds steam reforming – 36th month
D4.3 2 pantent applications – 36th month
D4.4 1 ISI article – 36th month
Phase no.
5
Phase title
Consortium management activities
Involved partners
CO
INCDTIM
Total
Person-months
33
33
Start month
1
End month
36
Objectives
O5.1 Coordination of Consortium activities
Description of work (possibily broken down into tasks) and role of participants
A 5.1 Ensure good communication between partners, organize the partners meetings and workshops.
A 5.2 Manage the overall project plan and assure the good timing of partners activities.
A 5.3 Manage the exploitation of the generated results and information; assure the attribution of the intellectual property rights in accordance with the Colaboration agreement.
A 5.4 Prepare and edit the scientific and economic reports for each project phase.
Deliverables (brief description and month of delivery)
D5.1 Detailed work plan
D5.2 Scientific and economic reports for each phase – 4 reports
D5.3 Final report
Table 3: Deliverables List
Deliverable No.
Deliverable Name
Phase no.
Type of Deliverable*
Phase delivery date
(1 ... n)
D1.1
Preparation method for mixed catalysts
1
Method
8th month
D1.2
Alumina supported Ni based mixed catalysts samples complete characterized from morphological and structural point of view
1
Product samples
8th month
D1.3
Report for evaluation of ethanol and glycerol steam reforming processes for hydrogen production and conceptual layout
1
Report
8th month
D1.4
Optimized method for bioethanol production from wood waste
1
Method
8th month
D1.5
Report of energetic valorization of biomass wastes
1
Report
8th month
D2.1
Bioethanol obtained and characterized
2
Product samples
18th month
D2.2
Report of evaluation by modeling and simulation of bioethanol steam reforming processes for hydrogen production
2
Report
18th month
D2.3
Technological parameters for laboratory scale H2 production by steam reforming of crude bioethanol obtained from wood waste
2
Technical report
18th month
D2.4
2 papers in international recognized journals (ISI ranked)
2
Article
18th month
D2.5
3 presentations at an international scientific meeting
2
Conference presentation
18th month
D3.1
Partialy purified waste glycerol solutions – starting with 24th month
3
Product Samples
32nd month
D3.2
Report of evaluation by modeling and simulation of glycerol steam reforming processes for hydrogen production
3
Report
32nd month
D3.3
Technological parameters for laboratory scale H2 production by steam reforming of waste glycerol solutions from biodiesel fabrication
3
Technical report
32nd month
D3.4
Experimental set-up for hydrogen production from waste glycerol solutions
3
Laboratory instalation
32nd month
D3.5
2 papers in international recognized journals (ISI ranked)
3
Article
32nd month
D3.6
2 presentations at an international scientific meeting
3
Conference presentation
32nd month
D4.1
Laboratory scale technology for hydrogen production from waste glycerol solutions resulted in biodiesel fabrication – 36th month
4
Technology
36th month
D4.2 Techno-economic and environmental impact evaluations of hydrogen production by hydroxylic compounds steam reforming
4
Report
36th month
D4.3
2 pantent applications
4
Patent
36th month
D4.4
1 ISI article – 36th month
4
Article
36th month
D5.1
Detailed work plan
1
Work plan
2nd month
D5.2
Scientific and economic reports for each phase – 4 reports
1,2,3,4
Phase report
Phase1–8th month
Phase2–18th month
Phase3–32nd month
Phase4–36th month
D5.3
Final report
4
Report
36th month
* according to Annex 6 – results indicators of the Programme (patent, technology, article etc)
Implementation
(max 10 pages)
2.1. Management structure and procedures
Project management involves the coordination of research among the 5 partners, the delivery of all outputs through the activities of the phases, as well as the organization of meetings and project communication. The project management structure will ensure that deadlines are met and that financial information including cost-statements is submitted and audit certificates obtained. The management structure is illustrated in the figure below as a hierarchical structure, but this is for project accountability purposes; the equality and integrity of all academic and economic partners in the project is respected.
Accountability line
Communication line
Figure 1. Project accountability and communication hierarchy.
The management structure of the project will consist of:
a. Steering Group – formed by the coordinators of each partner institution in the consortium. This group will meet several times during the time span of the project in order to oversee and take all key decisions on the progress of the research, including methodological issues, ethical issues, outcomes and dissemination. These meetings will be scheduled as follows: a meeting at the beginning of the project (month 2), a meeting corresponding to each phase (month 9, 19, 33), and a meeting at the end of the project. Two steering group meetings will coincide with 2 broader meetings of all the researchers involved. The steering group will monitor progress against agreed milestones and oversee deliverables. It will resolve any problems arising from the project, and will meet in emergency sessions, either through telephone/video conferences or additional meetings where necessary.
b. Coordinator. INCDTIM as the coordinator of the project will take responsibility for the overall project coordination and for liaising with the National Authority of Scientific Research. The coordinator has extensive experience of project management, including international projects. It will be responsible for organizing 5 steering group meetings, maintaining communication with partners, ensuring there is a shared understanding of the work, coordinating the activities during the established phases and ensuring deadlines are met and deliverables are produced. It will ensure that the project is undertaken in accordance with the highest standards of research ethics and scientific quality.
Timetables are crucial to the successful achievement and dissemination of research. The role of the coordinator is thus important, in particular to the maintenance of regular contact, both electronically and by regular meetings. INCDTIM will ensure that regular communication takes place between all partners. The coordinator has responsibility for monitoring work outputs and will establish internal deadlines for draft and final versions of reports.
c. Decision-making process. The key decision-making body is the project steering group, which will oversee the implementation of research objectives and milestones. In certain circumstances additional decisions may have to be taken at short notice by the project coordinator and reported to the partners.
d. Meetings. In addition to the steering group meetings all researchers will meet in 2 one day workshops, in month 2 and 19. This will allow all researchers to have an input into the project and to engage in key discussions on methods and project development. The first research workshop will set out the detailed research methodology, establish common ground rules and ethical guidelines; confirm milestones and detailed timetables. The 2nd workshop will focus on critical analysis towards the development of the catalytic steam reforming process of bioethanol and the development of the waste glycerol steam reforming process for H2 production will be discussed. Moreover, this meeting will ensure continued consensus about research objectives and project outcomes and consistency in presentation of results. The 6 project meetings (4 steering group meetings and 2 workshops) will all take place in Cluj-Napoca, the home city of 4 from among the 5 partners of the consortium, at INCDTIM, the coordinating institution.
e. Communication during the project will be both internal, as well as external. Internal Communication involves communication (electronic or phone) among partners between 2 consecutive meetings in order to allow information to be shared on a regular basis, as well as to ensure consultation on key issues. The communication language will be Romanian. External Communication includes communication with the National Authority for Scientific Research through reports as scheduled, as well as with the interested public through the project website. The Project website will be the public face of the project, where information of interest regarding the project will be submitted on a regular basis.
f. Consortium Agreement. Before the start of the project a Consortium Agreement will be signed by its members. This Agreement will cover the following issues: management of knowledge, research and innovation activities, a code of conduct addressing copyright and intellectually property right issues, ethical issues, and scientific quality standards.
2.2. Individual participants
CO – INCDTIM is a national research institute dedicated to research and development in natural sciences and engineering. The research activity unrolled in the Institute is developed on the following directions: (i) fundamental research in physics of stable isotopes, molecular physics, biophysics, solid state physics; (ii) applied research: separation of stable isotopes; applications of isotopic labeled compounds; preparation and characterization of nanostructured systems; catalysis; investigation at molecular level of the processes occurring in ecosystems; modern spectroscopic techniques for the investigation of composition and structure.
INCDTIM will participate in this project with its expertise in H2 production by catalytic steam reforming processes. The team involved has experience and expertise in catalytic methane steam reforming (see the project leader CV) which imply: catalysts preparation, catalysts characterization, performing of catalytic reactions, catalysts deactivation studies, etc. Some preliminary results were also obtained in ethanol catalytic steam reforming. The heterogeneous catalysis team coordinated 3 national and 2 international projects in the last years in the area of H2 production from CH4, H2 storage and environmental catalysis.
P1 – Babes-Bolyai University (UBB) is an academic educational public institution aiming to promote and sustain the development of specific cultural components within the national and international community. UBB is ranked within the first 2 universities of Romania taking into account the research activity. In the proposed project UBB will be involved with the Faculty of Chemistry and Chemical Engineering, Department of Chemical Engineering and Oxide Materials Science, Thus, the team of P1-UBB will be involved with its expertise in advanced modeling and simulation in energy conversion processes (e.g. catalytic steam reforming, gasification, combustion), H2 production and purification processes, chemical engineering expertise, model validation with experimental data collected from the project partners, complex process integration schemes for improvement of energy efficiency, techno-economic and environmental impact evaluations etc.
P2 – INCDO-INOE 2000, ICIA, is a national research institute dedicated to applied analytical chemistry in three main directions: bioenergy – biofuels, analytical instrumentation, and analytical chemistry of the environment. It has two laboratories with RENAR accreditation: laboratory for biofuel quality certification (CABIO) and environmental analysis laboratory (LAM). Based on the previous experience of ICIA, its main task in the present project is to develop and optimize the technology for bioethanol obtaining, using an acid hydrolysis of wood waste, enzymatic hydrolysis and a combination of simultaneous saccharification and fermentation of cellulosic waste. The research activities will focus on ecological pre-treatment of feedstocks, and hydrolysis and fermentation of woody biomass to the conversion of biomass into fuel ethanol and the bioethanol characterization according to SR EN 15376.
P3 –S.C. REVIVA Import Export S.R.L. Apahida, Cluj, is a SME working since 2002 with significant results in the area of food industry. The main products are soy based foods produced using an original REVIVA technology. Another direction of REVIVA activity is the production of soy oil and its use to produce biodiesel. REVIVA was involved in a Parteneriate 2008 research project - “Biofuels production by valorization of secondary products resulted in vegetable proteins fabrication”, resulting in an original technology named BIOVALP. The present project proposal is a continuation of the researches in this direction through valorization of glycerol wastes resulted in BIOVALP technology. REVIVA will participate with activities for: optimization of biodiesel production to result washing waters with higher glycerol concentrations, the analysis and partial purification of glycerol wastes.
P4 – SC ROKURA SRL is a SME involved since 1992 in communication projects, data acquisition and distance transmission, H2 rich gas production, energetic valorization of biomass. ROKURA has 2 major development directions: (i) monitoring and automation of industrial processes, and (ii) H2 rich gas production through aqueous-alkaline solutions, and cogeneration, based on biogas sources, biomass gasification, biomass direct combustion, and natural gas. In this project ROKURA will participate with activities related to design and realization of experimental set-up, experimentation and optimization of H2 production technology from biomass wastes.
The project leader is Senior Researcher Dr. Mihaela Diana Lazar, who received the PhD degree in chemistry at Babes-Bolyai University, Cluj-Napoca with the thesis “Studies of supported metal catalysts by H/D isotopic exchange”. Dr. Mihaela Diana Lazar has 12 years of experience in heterogeneous catalysis involving: (1) preparation of supported metal catalysts using various methods: impregnation, coprecipitation, deposition-precipitation, sol-gel technique; (2) catalysts characterization by determination of total surface area and metal surface area (BET method, chemisorption), particles size (TEM, XRD), metal oxidation state (XPS); (3) surface reactions by temperature-programmed techniques: desorption (TPD), reduction (TPR), oxidation (TPO); (4) determination of catalytic parameters (activity, selectivity, deactivation rate, carbon deposition, re-activation) in heterogeneous catalytic processes (hydrogenations, H/D isotopic exchange, steam reforming, water-gas shift, NOx reduction, etc). The most important results were obtained in the areas of: H2 production and storage; the study of hydrogen adsorption, activation and spillover on oxide supported gold catalysts using H/D isotopic exchange; the study of isocyanide adsorption on gold surface; catalytic properties of non-nanostructured gold; nanocarbon structures prepared by catalytic techniques. Dr. Mihaela Diana Lazar coordinated 3 research projects: (1) PN II “Parteneriate” Program: “Research and Development of a membrane reactor for ultra pure H2 production for fuel cells applications” (2007-2010); (2) Romania–Dubna, Russia Agreement; Theme: “Investigations of Nanosystems and Novel Materials by Neutron Scattering Methods” (2009-2011); and (3) NUCLEU Program: “Multifunctional nanostructured molecular systems” – coordinator of the heterogeneous catalysis topic (2003-2005). Moreover, she participated as team member in: 3 “CEEX” projects, 2 “PN II Parteneriate” projects, 3 “PN II Idei” projects; 2 international projects (one in INCDTIM Cluj-Napoca, and one at the Iowa State University).
The team from INCDTIM also includes: one senior researcher CSI Dr. Eng. Valer Almăşan, 3 PhD students and two technicians.
Assoc. Prof. Eng. Dr. Calin – Cristian Cormos will coordinate research team from P1-UBB. He has got his PhD degree in 2004 in chemical engineering.. He has more than 15 years of experience with scientific research, having also experience as a chemical engineer, plant manager and product development manager in chemical and pharmaceutical sector. He is responsible for 4 academic disciplines in chemical engineering, and published 62 scientific articles in international journals and peer-review conferences devoted to energy conversion. He coordinated or was involved in several national or international research projects in the field of energy with carbon capture and storage. Also, he is working as scientific referent for prestigious international journals and is involved as project evaluator for national and international (e.g. FP7) project competitions. The team proposed by UBB also includes: one Lecturer, Dr. Ana-Maria Cormos, one associated professor and one professor.
Senior researcher Dr. Cecilia Roman will lead the research team from P2-ICIA. She has got her PhD degree in 1997 from UBB Cluj-Napoca, and is currently the head of Research Department of ICIA. Her rich scientific experience includes technologies for bioethanol obtaining from lignocellulosic biomass. She coordinated 10 national projects, and was responsible for other 10, from which 3 are international ones. She is author of 2 patents, 3 books, 52 ISI articles, and participated at more than 90 national and international conferences.
The team proposed by ICIA also includes: 1 scientific researcher and 1 PhD Student.
Eng. Koncz Carol will coordinate the research team from P3-REVIVA. He is currently the head of Technical Department at SC REVIVA SRL. His experience includes: fabrication of protein texture from soybean, fabrication of soy oil, fabrication of biofuels from soy oil. He coordinated one research project in PN II Parteneriate Program.
The team of SC REVIVA SRL also includes: 1 engineer and 1 economist.
Dr. Eng. Petcu Cristian Mihai will lead the research team from P4 ROKURA. He has got his PhD degree in 1998 in engineering in the field of thermal engines. His current position is R&D and Scientific manager at SC ROKURA SRL. His work experience includes: renewable energy projects, co-generation system projects, hydrogen combustion in engines, producing of hydrogen rich gas for fuels treatment. He coordinated 4 research projects in PN II Parteneriate program. The team of SC ROKURA SRL also includes: 3 engineers and 1 PhD student.
2.3. Consortium as a whole
The consortium involved in the implementation of this project proposal is well balanced between 2 National Institutes of Research and Development: INCDTIM as coordinator (CO) and INCDO-INOE 2000, ICIA as P2, 1 Romanian top university, Babes-Bolyai University, Cluj-Napoca as P1, and 2 economic companies: SC REVIVA SRL, Cluj-Napoca as P3, specialized in biodiesel fabrication, and SC ROKURA SRL, Bucuresti as P4, implied in alternative energy market. The proposed research approach requires a multidisciplinary team, thus the involved partners of the Consortium comprise experts in the fields of heterogeneous catalysis, chemical engineering, biomass processing, process optimization and integration, control and automation of industrial processes, etc.
The project will be highly interactive, all partners being involved with very specific tasks which are interconnected and in most cases interdependent. All partners have demonstrated the ability to co-operate productively with other consortium members and most have collaborated previously, either with each other or with the coordinator.
The available infrastructure at each partner institution ensures the successful achievement of most specific tasks scheduled in the workplan (see “Available research infrastructure” section). Thus, equipment available at CO ensures catalyst preparation, characterization and testing; IT infrastructure available at P1 will be used for process modelling and simulation; analysis infrastructure at P2 will be used for bioethanol and waste glycerol characterization, while the fermentation equipment will be used for bioethanol production; P3 has all the equipment for the preparation of biodiesel (crude glycerol is a biodiesel waste); IT infrastructure available at P4 will be used for the design of experimental set-up, scale-up, etc. However, several equipments will also be purchased in order to improve the research infrastructure.
The project objectives presented in Section 1.1 imply the activity and commitment of all partners. Based on the previous results obtained by the consortium members in collaborative research projects we have all the reasons to affirm that the partners will create a strong research network which incorporates all the necessary expertise in biomass transformation in hydroxylic compounds, catalytic studies for H2 production, chemical engineering, mathematical modeling of chemical processes, design and elaboration of laboratory technology, project and financial management required to meet the project objectives.
2.4. Resources to be committed.
Successful development of the project requires the commitment of the following resources:
Human resources involved in the project comprise specialists of various qualifications in accordance with the multidisciplinary character of the topic proposed. Each partner institution of the consortium will involve a research team consisting in both senior researchers and young ones. The involved personnel are in accordance with the implication of each partner in the development of the project.
Involved partner
CO
P1
P2
P3
P4
Total
Person-months
145
53
82
15
46
341
Infrastructure resources include all the available equipment at each partner institution as presented in the “Available research infrastructure” section. However, an integrated system for catalyst characterization and a gas chromatograph for the online analysis of reaction products will be purchased.
Financial resources necessary for the implementation of the project include both finances from the Public Budget (92.5%) and Private cofinancing (7.5%). The total budget is of 3.243.400 lei, which will be divided by destination as presented in the table below.
Personnel costs
Logistics
Travel
Indirect Costs
Equipments
Materials
Subcontracting
54.7%
14.6%
11.7%
0.6%
2%
16.4%
Time resources refer to the available time for the implementation of the project. The project is meant to be accomplished in 36 months. The allocated time for the development of each phase is in good agreement with the complexity and amount of the activities involved.
2.5. Methodology and associated work plan:
The main objective of this project proposal is to develop a laboratory scale technology and experimental set-up for the production of hydrogen by steam reforming of hydroxylic compounds (monohydroxylic alcohols and glycerol) resulted as wastes in biomass processing or prepared from waste of biomass. All efforts will be concentrated towards the obtaining of the main end product of the project that is the experimental set-up and catalytic technology for hydrogen production from waste glycerol correlated with techno-economical and environmental impact assessments.
Work Plan Strategy. The work plan will be delivered in four research-development (RD) phases, each with demonstrable deliverables, while a fifth phase of project management and coordination will support the previous four phases (Table 1).
Figure 2. HYCAT Work Plan.
A detailed description of the phases is presented below.
Phase 1 (month 1 to 8) aims to set a solid foundation for the development of the entire project. Thus, research activities will focus on the preparation and characterization of novel mixed catalysts based on alumina and zirconia supported Ni, promoted by either noble metals (Au, Ag, Pt, Rh) or rare earth oxides (La2O3, CeO2, Y2O3), after a thorough literature survey. Thermodynamic analysis of ethanol and glycerol steam reforming processes by evaluating the influence of process parameters such as temperature, pressure and catalyst on the conversion rates, and reaction products will ensure the basis for the future development of the proposed technology. Conceptual layout of the steam reforming process will be discussed and established by the involved partners. Hydrogen production by steam reforming of renewable oxygenates is basically economically feasible if H2 yields are high and if catalysts can be used in numerous catalytic cycles without loss of activity. Thus, optimization of bioethanol production in order to obtain a product as clean as possible for future use in steam reforming will be accomplished. A thorough study aiming the investigation of energetic valorization of biomass wastes will also be presented.
Phase 2 (month 9 to 18) will focus on developing a technology for H2 production by catalytic steam reforming of bioethanol obtained from wood waste. Thus, catalysts prepared in the previous phase will be tested in EtSR reaction (atmospheric pressure, and reaction temperature in the range 200-400°C) and reaction parameters such as ethanol conversion, H2 selectivity, H2 yield, and catalyst deactivation will be established. Based on the information provided by P2-ICIA in charge of optimizing the bioethanol production process and of characterizing the product from the physico-chemical point of view, a reactant ratio ethanol-water as similar as possible with the bioethanol product, will be used. Catalysts demonstrating maximum conversion and minimum catalyst deactivation in EtSR will be further used in the bioethanol steam reforming process. Meanwhile, partner P1-UBB will perform mathematical modeling and simulation of bioethanol steam reforming process using specific software (ChemCad, AspenPlus). Model validation will be performed using the experimental data obtained by CO-INCDTIM in the bioethanol steam reforming process.
Phase 3 (month 19 to 32) is the key phase of the project aiming the development of a technology for H2 production by waste glycerol catalytic steam reforming. Thus, prepared catalysts will be tested in the GlySR reaction (atmospheric pressure, and reaction temperature in the range 500-700°C) by CO-INCDTIM, and reaction parameters will be established for maximum glycerol conversion, and maximum H2 selectivity and yield. The experimental set-up will be configured in such a way as to permit analysis of both gaseous and liquid reaction products. A special attention will be paid to the enhancement of the catalyst life time by studying the catalyst deactivation process. Deposited coke will be characterized by several techniques (TGA, TPO, and TEM) in order to establish a correlation between type and amount of deposited coke, catalyst nature and reaction conditions. All these will enhance the economic efficiency of the hydrogen production process. Raw material for the process will be provided by P3-Reviva, after optimization of their original BIOVALP technology for biodiesel production in order to obtain wastes with higher concentrations of glycerol. Moreover, provided raw material will be fully characterized from the chemical composition point of view in colaboration with P2-ICIA. Compounds with possible poisoning effect on the catalyst will be identified and separated from the waste glycerol solutions. For the separation of the reaction product of interest – H2, a hydrogen separator based on a Pd membrane will be designed, and tested by the CO-INCDTIM. P1-UBB will perform the mathematical modeling and simulation of the waste glycerol steam reforming process using dedicated software packages (ChemCad, AspenPlus) and validate the model using the experimental data provided by CO-INCDTIM. Process integration issues (mass and energy) will also be addressed. P4-ROKURA in collaboration with CO-INCDTIM will design and test the experimental set-up for using a greater amount of catalyst for the waste glycerol steam reforming process that is 10-50 g of catalyst.
Phase 4 (month 33 to 36) aims a thorough analysis of the developed laboratory scale technology from the techno-economical, environmental and scale-up point of view. Achievement of these goals implies the involvement of each partner of the consortium. Potential implementation of the developed technology will be also investigated and proposed.
Phase 5 (month 1 to 36) covers the management and scientific coordination and will last for the entire duration of the project. Activities include project management, the organisation of four steering group meetings and two workshops, ensuring communication between partners and with the National Authority for Scientific Research, ensuring a shared understanding of the work and timetables, as well as submitting scientific and financial reports.
Planning timetable of the HYCAT project is presented below, with the timing for each phase and each activity (see Table 2 Phase description for each activity description).
Figure 3. GANT diagram of the HYCAT project.
Each phase will provide a series of deliverables such as: methods, products, scientific and technical reports, laboratory technology, papers, conference presentations, and patents (see Table 3. Deliverables List).