THESIS
Kinetic Study of Catalytic Partial Oxidation of
Synthetic Diesel for Hydrogen Production
University of Regina
Faculty of Graduate Studies and Research, University of Regina
A Thesis Submitted to the Faculty of Graduate Studies and Research In Partial
Fulfillment of the Requirements for the Degree of Master of Applied Science in
Process Systems Engineering, University of Regina. xix, 152 p.
Khan, Md. Faysal Ahamed
Jan-2012
Master of Applied Science (MASc)
Faculty of Engineering and Applied Science
Engineering - Process Systems
Abstract:
The focus of this research is to study the
kinetics of the catalytic partial oxidation
(CPOX) of synthetic diesel (SD) for hydrogen production. The kinetic
experiments were done in a packed bed tubular reactor (PBTR) over a 5wt.%Ni/Ce0.5Zr0.33Ca0.085Y0.085
(5N/CZCaY) catalyst prepared by a surfactant-assisted route. The SD is composed
of 75 vol.% saturated hydrocarbons and
25 vol.% aromatic hydrocarbons, with an average
chemical formula resembling commercial diesel C12.87H24.81. The kinetic
experiments were conducted at
atmospheric pressure, in the temperature range of 1123-1223K (850- 950 degrees C), with oxygen/synthetic diesel
(O2/SD) ratio in the range of 6.7-10.5 and W/FSD,0 weight-time) in the range of
19008-47556 kgcatalyst*s/kmolSD. The experimental results were used to derive
an empirical power law rate model. This model was of the form: r'SD =
K0e(-E/RT)NmSDNn02
Activation energy was found to be 16kJ/mol and
the order of reaction with respect to SD was 1.89 (≈2) and with respect to
oxygen was found to be 0.41 (≈1/2). Estimation of the values of the model
parameters was based on the minimization of the sum of the residual squares of
the reaction rates by Gauss-Newton and
Levenberg-Marquardt algorithm using non-linear regression (NLREG)
software. Excellent agreement between
the experimental and predicted rate was established with an absolute average deviation (AAD) of 8%. The
5N/CZCaY catalyst was tested for an
extended time on stream (TOS) operation in order to establish and
demonstrate that the catalyst is stable
and also to ensure steady state performance. In addition, the effects of
reaction parameters such as reaction temperature, feed ratio (O2/SD), and
weight-time W/FSD,0) on the resultant catalytic activity of the chosen catalyst
were also investigated in order to obtain the optimal operating conditions for
H2 production from CPOX of SD. To the best of our knowledge, the current study
is the first of its kind on the CPOX reforming of SD.
Free Full Text Source: http://dspace.cc.uregina.ca:8080/dspace/handle/10294/3542
Tuesday, December 4, 2012
HERCULES A-B-C, A 10-Year Major R&D Effort Towards the Next Generation Large Marine Diesel Engines
Procedia - Social and Behavioral Sciences, Volume 48, 2012, Pages
1068–1077
Transport Research Arena 2012
HERCULES A-B-C, A 10-Year Major R&D Effort Towards the Next Generation Large Marine Diesel Engines
Nikolaos P. Kyrtatos
National Technical University of Athens, Laboratory of Marine Engineering, P.O.Box 64501, Athens 15704, Greece
Abstract
In 2004, the Integrated project I.P.HERCULES (High Efficiency Engine R&D on Combustion with Ultra Low Emissions for Ships) was funded within EC/FP6, with the major engine makers MAN & WARTSILA, which together hold 90% of the world market and 40 other industrial & university partners. It was the 1st phase of the HERCULES R&D program on large engine technologies. The I.P. HERCULES (A) was broad in the coverage of the various R&D topics and considered a range of options and technologies.
HERCULES- B was Phase II of the Program, running from 2008 to 2011, with 32 participant organizations and 26 M€ budget, funded by FP7. The general targets for emissions and fuel consumption were retained in HERCULES-B. However, based on the developed know-how and results of I.P. HERCULES (A), it was possible to narrow down the search area, to focus on potential breakthrough research and to further develop the most promising techniques for lower specific fuel consumption (and CO2 emissions) and ultra-low gaseous and particulate emissions.
For taking marine engine technology a step further towards improved sustainability in energy production and total energy economy, an extensive integration of the multitude of new technologies identified in Phase I and Phase II of HERCULES is required.
The HERCULES-C project (2012-2015) with 22 participant organizations and 17 M€ budget, is the Phase III of the HERCULES programme and adopts a combinatory approach for engine thermal processes optimization, system integration, as well as engine reliability and lifetime.
This paper provides an overview of the complex structure, as well as the main achievements of the HERCULES R&D programme.
Free Full Text Source: http://www.sciencedirect.com/science/article/pii/S1877042812028194
Transport Research Arena 2012
HERCULES A-B-C, A 10-Year Major R&D Effort Towards the Next Generation Large Marine Diesel Engines
Nikolaos P. Kyrtatos
National Technical University of Athens, Laboratory of Marine Engineering, P.O.Box 64501, Athens 15704, Greece
Abstract
In 2004, the Integrated project I.P.HERCULES (High Efficiency Engine R&D on Combustion with Ultra Low Emissions for Ships) was funded within EC/FP6, with the major engine makers MAN & WARTSILA, which together hold 90% of the world market and 40 other industrial & university partners. It was the 1st phase of the HERCULES R&D program on large engine technologies. The I.P. HERCULES (A) was broad in the coverage of the various R&D topics and considered a range of options and technologies.
HERCULES- B was Phase II of the Program, running from 2008 to 2011, with 32 participant organizations and 26 M€ budget, funded by FP7. The general targets for emissions and fuel consumption were retained in HERCULES-B. However, based on the developed know-how and results of I.P. HERCULES (A), it was possible to narrow down the search area, to focus on potential breakthrough research and to further develop the most promising techniques for lower specific fuel consumption (and CO2 emissions) and ultra-low gaseous and particulate emissions.
For taking marine engine technology a step further towards improved sustainability in energy production and total energy economy, an extensive integration of the multitude of new technologies identified in Phase I and Phase II of HERCULES is required.
The HERCULES-C project (2012-2015) with 22 participant organizations and 17 M€ budget, is the Phase III of the HERCULES programme and adopts a combinatory approach for engine thermal processes optimization, system integration, as well as engine reliability and lifetime.
This paper provides an overview of the complex structure, as well as the main achievements of the HERCULES R&D programme.
Free Full Text Source: http://www.sciencedirect.com/science/article/pii/S1877042812028194
Adsorption Behavior of Metal–Organic Frameworks for Thiophenic Sulfur from Diesel Oil
Ind. Eng. Chem. Res., 2012, 51 (38), pp 12449–12455
Adsorption Behavior of Metal–Organic Frameworks for Thiophenic Sulfur from Diesel Oil
Hong-Xing Zhang †§, Hong-Liang Huang ‡§, Chun-Xi Li *†§, Hong Meng §, Ying-Zhou Lu §, Chong-Li Zhong ‡§, Da-Huan Liu ‡§, and Qing-Yuan Yang ‡§
licx@mail.buct.edu.cn
† State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China
‡ State Key Laboratory of Organic−Inorganic Composites, Beijing University of Chemical Technology, Beijing, 100029, China
§ College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, China
Abstract
Researchers synthesized four metal–organic frameworks (MOFs) using two different metal centers and two different organic ligands, viz., Cu3[C6H3(CO2)3]2 (Cu-BTC), Cu[O2C–C6H4–CO2] (Cu-BDC), Cr(OH)[O2C–C6H4–CO2] (Cr-BDC), and Cr3F(H2O)3O[C6H3(CO2)3]2 (Cr-BTC). They studied their adsorption behaviors for thiophenic sulfurs in model diesel oils at mild temperatures. Adsorption follows the order Cu-BTC > Cr-BDC > Cr-BTC
Cu-BDC.
The adsorption capacity of various sulfur compounds follows the order dibenzothiophene (DBT) > benzothiophene (BT) > 3-methylthiophene (3-MT). The MOFs adsorption mechanism is regarded as a combined effect of many factors involving appropriate framework structure, suitable pore size and shape, and exposed Lewis acid site matching the S-compound to be adsorbed. The difference in adsorptive activity among the organosulfurs is mainly ascribed to their π-electron number and the electron density on the S-atom. The used MOF can be easily regenerated by solvent washing and recycled at least five times.
Full Text Source (Subscription or Fee): http://pubs.acs.org/doi/abs/10.1021/ie3020395
Adsorption Behavior of Metal–Organic Frameworks for Thiophenic Sulfur from Diesel Oil
Hong-Xing Zhang †§, Hong-Liang Huang ‡§, Chun-Xi Li *†§, Hong Meng §, Ying-Zhou Lu §, Chong-Li Zhong ‡§, Da-Huan Liu ‡§, and Qing-Yuan Yang ‡§
licx@mail.buct.edu.cn
† State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China
‡ State Key Laboratory of Organic−Inorganic Composites, Beijing University of Chemical Technology, Beijing, 100029, China
§ College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, China
Abstract
Researchers synthesized four metal–organic frameworks (MOFs) using two different metal centers and two different organic ligands, viz., Cu3[C6H3(CO2)3]2 (Cu-BTC), Cu[O2C–C6H4–CO2] (Cu-BDC), Cr(OH)[O2C–C6H4–CO2] (Cr-BDC), and Cr3F(H2O)3O[C6H3(CO2)3]2 (Cr-BTC). They studied their adsorption behaviors for thiophenic sulfurs in model diesel oils at mild temperatures. Adsorption follows the order Cu-BTC > Cr-BDC > Cr-BTC
The adsorption capacity of various sulfur compounds follows the order dibenzothiophene (DBT) > benzothiophene (BT) > 3-methylthiophene (3-MT). The MOFs adsorption mechanism is regarded as a combined effect of many factors involving appropriate framework structure, suitable pore size and shape, and exposed Lewis acid site matching the S-compound to be adsorbed. The difference in adsorptive activity among the organosulfurs is mainly ascribed to their π-electron number and the electron density on the S-atom. The used MOF can be easily regenerated by solvent washing and recycled at least five times.
Full Text Source (Subscription or Fee): http://pubs.acs.org/doi/abs/10.1021/ie3020395
A novel method for improving the physicochemical properties of diesel and jet fuel using polyaspartate polymer additives
Fuel, Available online 25 October 2012, In Press, Uncorrected Proof
A novel method for improving the physicochemical properties of diesel and jet fuel using polyaspartate polymer additives
C.G. Tsanaktsidis a, S.G. Christidis a, E.P. Favvas b
a Laboratory of Qualitative Fuel Control, Department of Pollution Control and Technologies, Technological Education Institute of Western Macedonia, Kila, Kozani 50100, Greece
b Institute of Physical Chemistry, NCSR “Demokritos”, 153 40, Agia Paraskevi, Attikis, Greece
Abstract
Reports the use of Thermal Polyaspartate Anion, a derivative biopolymer of aspartic acid, to remove water residues of both diesel and jet liquid hydrocarbons fuels.
Authors describe a novel and simple method for improving fuel properties. They mixed various masses of TPA polymer with a constant volume of fuel. They determined the humidity concentration, the heat of combustion, the flash point as well the cetane index according to ASTM standard protocols. Water removal improved the physicochemical properties of both studied fuels, diesel and jet, up to 463 kJ/g and 1040 kJ/g for the heat of combustion, 28.2% and 71.4% for the total acid number and up to 39.4% and 25.7% for humidity, for diesel fuel and jet fuel respectively. The proposed method can be used in a simple fuel cleaning process using a metal mesh vessel of Thermal Polyaspartate Anion (TPA) polymer. The polymer can be replaced and re-generated as often needed.
Full Text Source (Subscription or Fee): http://www.sciencedirect.com/science/article/pii/S0016236112007892
A novel method for improving the physicochemical properties of diesel and jet fuel using polyaspartate polymer additives
C.G. Tsanaktsidis a, S.G. Christidis a, E.P. Favvas b
a Laboratory of Qualitative Fuel Control, Department of Pollution Control and Technologies, Technological Education Institute of Western Macedonia, Kila, Kozani 50100, Greece
b Institute of Physical Chemistry, NCSR “Demokritos”, 153 40, Agia Paraskevi, Attikis, Greece
Abstract
Reports the use of Thermal Polyaspartate Anion, a derivative biopolymer of aspartic acid, to remove water residues of both diesel and jet liquid hydrocarbons fuels.
Authors describe a novel and simple method for improving fuel properties. They mixed various masses of TPA polymer with a constant volume of fuel. They determined the humidity concentration, the heat of combustion, the flash point as well the cetane index according to ASTM standard protocols. Water removal improved the physicochemical properties of both studied fuels, diesel and jet, up to 463 kJ/g and 1040 kJ/g for the heat of combustion, 28.2% and 71.4% for the total acid number and up to 39.4% and 25.7% for humidity, for diesel fuel and jet fuel respectively. The proposed method can be used in a simple fuel cleaning process using a metal mesh vessel of Thermal Polyaspartate Anion (TPA) polymer. The polymer can be replaced and re-generated as often needed.
Full Text Source (Subscription or Fee): http://www.sciencedirect.com/science/article/pii/S0016236112007892
Selective adsorption for removing sulfur: a potential ultra-deep desulfurization approach of jet fuels
RSC Adv., 2012,2, 1700-1711
Selective adsorption for removing sulfur: a potential ultra-deep desulfurization approach of jet fuels
Yuesong Shen , Peiwen Li , Xinhai Xu and Hong Liu
1. College of Materials Science and Engineering,State Key Laboratory of Materials-Oriented Chemical Engineering,Nanjing University of Technology, Nanjing, PR China
2. Department of Aerospace and Mechanical Engineering,The University of Arizona, Tucson, USA
Through appropriate reforming and shifting processing, jet fuels can be converted into syngas, a suitable fuel for solid oxide fuel cells for many auxiliary and backup power units. Integrated micro fuel processors in combination with solid oxide fuel cell (SOFC) stacks using jet fuels are promising as portable power sources. Because the sulfur in jet fuels causes catalyst poisoning for fuel processing reactions and the electrochemical reactions in fuel cells, ultra-deep sulfur removal in jet fuels and other hydrocarbon fuels is extremely important.
Selective adsorption for removing sulfur (SARS) is an emerging state-of-the-art technology. SARS is promising because it obtains ultra-deep desulfurization efficiency at ambient temperature and atmospheric pressure without hydrogen consumption. Authors survey the current status and prospect of the SARS technology for jet fuels. They discuss important issues yet to be resolved for the SARS technology.
Full Text Source (Subscription or Fee): http://pubs.rsc.org/en/content/articlelanding/2012/ra/c1ra00944c/unauth
Selective adsorption for removing sulfur: a potential ultra-deep desulfurization approach of jet fuels
Yuesong Shen , Peiwen Li , Xinhai Xu and Hong Liu
1. College of Materials Science and Engineering,State Key Laboratory of Materials-Oriented Chemical Engineering,Nanjing University of Technology, Nanjing, PR China
2. Department of Aerospace and Mechanical Engineering,The University of Arizona, Tucson, USA
Through appropriate reforming and shifting processing, jet fuels can be converted into syngas, a suitable fuel for solid oxide fuel cells for many auxiliary and backup power units. Integrated micro fuel processors in combination with solid oxide fuel cell (SOFC) stacks using jet fuels are promising as portable power sources. Because the sulfur in jet fuels causes catalyst poisoning for fuel processing reactions and the electrochemical reactions in fuel cells, ultra-deep sulfur removal in jet fuels and other hydrocarbon fuels is extremely important.
Selective adsorption for removing sulfur (SARS) is an emerging state-of-the-art technology. SARS is promising because it obtains ultra-deep desulfurization efficiency at ambient temperature and atmospheric pressure without hydrogen consumption. Authors survey the current status and prospect of the SARS technology for jet fuels. They discuss important issues yet to be resolved for the SARS technology.
Full Text Source (Subscription or Fee): http://pubs.rsc.org/en/content/articlelanding/2012/ra/c1ra00944c/unauth
SchIBZ - Design Of Different Diesel Based Fuel Cell Systems for Seagoing Vessels and Their Evaluation
ECS Trans. 2012 volume 42, issue 1, 49-58
SchIBZ - Design Of Different Diesel Based Fuel Cell Systems for Seagoing Vessels and Their Evaluation
Keno Leites a, Ansgar Bauschulte b, Michael Dragon c, Stefan Krummrich d and Pedro Nehter e
a Blohm + Voss Naval GmbH
b Oel-Waerme-Institut GmbH
c Helmut-Schmidt-Universität Hamburg
d Howaldtswerke-Deutsche Werft GmbH
e Topsoe Fuel Cell A/S
Abstract
The goal of the SchIBZ project is to develop and test a fuel cell based generator set for seagoing ships. A short study was conducted before the start of the system development to evaluate various solutions before choosing one.
This paper contains a short review of the possibilities and selected results.
Full Text Source (Subscription or Fee): http://ecst.ecsdl.org/content/42/1/49.short
SchIBZ - Design Of Different Diesel Based Fuel Cell Systems for Seagoing Vessels and Their Evaluation
Keno Leites a, Ansgar Bauschulte b, Michael Dragon c, Stefan Krummrich d and Pedro Nehter e
a Blohm + Voss Naval GmbH
b Oel-Waerme-Institut GmbH
c Helmut-Schmidt-Universität Hamburg
d Howaldtswerke-Deutsche Werft GmbH
e Topsoe Fuel Cell A/S
Abstract
The goal of the SchIBZ project is to develop and test a fuel cell based generator set for seagoing ships. A short study was conducted before the start of the system development to evaluate various solutions before choosing one.
This paper contains a short review of the possibilities and selected results.
Full Text Source (Subscription or Fee): http://ecst.ecsdl.org/content/42/1/49.short
Adsorptive Denitrogenation and Desulfurization of Diesel Fractions by Mesoporous SBA15-Supported Nickel(II) Phosphide Synthesized through a Novel Approach of Urea Matrix Combustion
Ind. Eng. Chem. Res., 2012, 51 (44), pp 14503–14510
Adsorptive Denitrogenation and Desulfurization of Diesel Fractions by Mesoporous SBA15-Supported Nickel(II) Phosphide Synthesized through a Novel Approach of Urea Matrix Combustion
Syed A. Shahriar , Hongfei Lin , and Ying Zheng *
yzheng@unb.ca
Department of Chemical Engineering, University of New Brunswick, 15 Dineen Drive, P.O. Box 4400, Fredericton, NB, Canada E3B 5A3
Abstract
One technique to promote the effectiveness of the conventional hydrodesulfurization (HDS) process is to remove the organic nitrogen-containing compounds from the feed before HDS. Researchers studied adsorptive removal of nitrogen compounds at room temperature and pressure without the presence of hydrogen using a high-capacity adsorbent, Ni2P/SBA15.
The adsorbent was prepared by the urea matrix combustion (UMxC) method. A metal loading of 7 wt % Ni was observed to be optimum among the loadings tested. The nitrogen adsorption capacity reached 9.1 mg/g of adsorbent. This is higher than the capacities of most of the reported adsorbents. The mesoporous nature of the adsorbent was confirmed by nitrogen adsorption/desorption analysis as well as TEM analysis. Solvent-washing regeneration was studied. After four adsorption-and-regeneration cycles approximately 95% of the adsorptive capacity of the sorbent was recovered.
Full Text Source (Subscription or Fee): http://pubs.acs.org/doi/abs/10.1021/ie3015044
Adsorptive Denitrogenation and Desulfurization of Diesel Fractions by Mesoporous SBA15-Supported Nickel(II) Phosphide Synthesized through a Novel Approach of Urea Matrix Combustion
Syed A. Shahriar , Hongfei Lin , and Ying Zheng *
yzheng@unb.ca
Department of Chemical Engineering, University of New Brunswick, 15 Dineen Drive, P.O. Box 4400, Fredericton, NB, Canada E3B 5A3
Abstract
One technique to promote the effectiveness of the conventional hydrodesulfurization (HDS) process is to remove the organic nitrogen-containing compounds from the feed before HDS. Researchers studied adsorptive removal of nitrogen compounds at room temperature and pressure without the presence of hydrogen using a high-capacity adsorbent, Ni2P/SBA15.
The adsorbent was prepared by the urea matrix combustion (UMxC) method. A metal loading of 7 wt % Ni was observed to be optimum among the loadings tested. The nitrogen adsorption capacity reached 9.1 mg/g of adsorbent. This is higher than the capacities of most of the reported adsorbents. The mesoporous nature of the adsorbent was confirmed by nitrogen adsorption/desorption analysis as well as TEM analysis. Solvent-washing regeneration was studied. After four adsorption-and-regeneration cycles approximately 95% of the adsorptive capacity of the sorbent was recovered.
Full Text Source (Subscription or Fee): http://pubs.acs.org/doi/abs/10.1021/ie3015044
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