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Claude Mirodatos - One of the best experts on this subject based on the ideXlab platform.

  • FCC of upgraded pyrolysis liquid mixed crude oil distillates: combined strategies for improving bio-fuel yields and quality
    2017
    Co-Authors: Y. Chapelliere, Yves Schuurman, Claude Mirodatos, A. Tuel, S. Wellach, E. Jordan
    Abstract:

    In order to meet the EU’s renewable energy targets by 2020 (up to 10% share in all forms of transportation fuels), a realistic alternative to first generation bio-fuels is to produce hybrid bio/fossil fuels by co-refining biomass pyrolysis liquids (PL) with crude oil fractions in a conventional oil refinery. However, co-refining may lead to severe changes in products quality, such as a higher aromaticity and residual oxygenates in the hybrid fuels that are produced. For the case of co-FCC (fluid catalytic cracking), various strategies can be implemented to limit those impacts along this complex value chain ranging from bio-mass to bio-gasoline. A first strategy was tested to preserve the gasoline yield and quality by implementing a PL hydrotreating prior to Co-Processing, to lower their oxygen content. By following the changes in conversion, yields and gasoline composition (aromatics/olefins vs saturated alkanes) as a function of the bio-oils hydrotreating severity, measured in a Micro Activity Test (MAT) reactor, it was shown that a compromise could be reached between bio-oil upgrading severity and FCC products yields and quality (RON, PIONA analysis). An optimum in the gasoline yields and quality was found by adding 10 to 25 wt.% of a mildly deoxygenated bio-oil to a standard VGO, via a Co-Processing carried out on a commercial equilibrated FCC catalyst. A second strategy was to adapt the FCC catalysts to the presence of oxygenate molecules typical of the bio-feedstock still present in the upgraded pyrolytic liquids. To that end, Y zeolites, which are the main active component in FCC catalysts, were up-graded by creating a mesoporosity in addition to the microporosity to favor the diffusion of the large lignocellulosic fragments throughout the cracking catalysts, according various hierarchical post synthesis processes. The main effects of replacing progressively micro- by meso-porosity are i) to slightly increase naphta yields (Fig. 1), ii) to decrease coke formation at high conversion (Fig. 2), iii) to increase the unsaturated fraction in gaseous (C3-C5) (Fig. 3) and liquid products (not shown here), and iv) to decrease markedly the remaining oxygenated products in the liquid fraction (mainly alcohols, acids and phenolics, from 31PNMR measurements). These effects underline the positive role of creating a mesoporosity in hierarchical FCC catalysts, in line with cracking mechanistic features. The combined impact for these two strategies on co-FCC will be discussed as a guideline for minimizing the cost of bio-oils upgrading and thereof the hybrid transportation fuels, while maintaining their quality within the specification limits. Acknowledgements This study is supported by the “FASTCARD” EU FP7-NMP-2013 (GA n° 604277)

  • second generation biofuels by co processing catalytic pyrolysis oil in fcc units
    Applied Catalysis B-environmental, 2014
    Co-Authors: Nicolas Thegarid, Gabriella Fogassy, Yves Schuurman, Claude Mirodatos, Stylianos D Stefanidis, E F Iliopoulou, Konstantinos G Kalogiannis, A A Lappas
    Abstract:

    Abstract Previous research showed that hydrodeoxygenated (HDO) pyrolysis-oils could successfully be co-processed with vacuum gasoil (VGO) in a labscale fluid catalytic cracking (FCC) unit to bio-fuels. Typically the hydrodeoxygenation step takes place at ∼300 °C under 200–300 bar of hydrogen. Eliminating or replacing this step by a less energy demanding upgrading step would largely benefit the FCC Co-Processing of pyrolysis oils to bio-fuels. In this paper a bio-oil that has been produced by catalytic pyrolysis (catalytic pyrolysis oil or CPO) is used directly, without further upgrading, in catalytic cracking Co-Processing mode with VGO. The results are compared to the Co-Processing of upgraded (via HDO) thermal pyrolysis oil. Though small but significant differences in the product distribution and quality have been observed between the Co-Processing of either HDO or CPO, they could be corrected by further catalyst development (pyrolysis and/or FCC), which would eliminate the need for an up-stream hydrodeoxygenation step. Moreover, the organic yield of the catalytic pyrolysis route is estimated at approximately 30 wt.% compared to an overall yield for the thermal pyrolysis followed by a hydrodeoxygenation step of 24 wt.%.

  • Second-generation biofuels by Co-Processing catalytic pyrolysis oil in FCC units
    Applied Catalysis B: Environmental, 2014
    Co-Authors: Nicolas Thegarid, Gabriella Fogassy, Yves Schuurman, Claude Mirodatos, Stylianos D Stefanidis, E F Iliopoulou, Konstantinos G Kalogiannis, A A Lappas
    Abstract:

    Previous research showed that hydrodeoxygenated (HDO) pyrolysis-oils could successfully be co-processed with vacuum gasoil (VGO) in a labscale fluid catalytic cracking (FCC) unit to bio-fuels. Typically the hydrodeoxygenation step takes place at similar to 300 degrees C under 200-300 bar of hydrogen. Eliminating or replacing this step by a less energy demanding upgrading step would largely benefit the FCC Co-Processing of pyrolysis oils to bio-fuels. In this paper a bio-oil that has been produced by catalytic pyrolysis (catalytic pyrolysis oil or CPO) is used directly, without further upgrading, in catalytic cracking Co-Processing mode with VGO. The results are compared to the Co-Processing of upgraded (via HDO) thermal pyrolysis oil. Though small but significant differences in the product distribution and quality have been observed between the Co-Processing of either HDO or CPO, they could be corrected by further catalyst development (pyrolysis and/or FCC), which would eliminate the need for an up-stream hydrodeoxygenation step. Moreover, the organic yield of the catalytic pyrolysis route is estimated at approximately 30 wt.% compared to an overall yield for the thermal pyrolysis followed by a hydrodeoxygenation step of 24 wt.%. (C) 2013 Elsevier B.V. All rights reserved.

  • the fate of bio carbon in fcc co processing products
    Green Chemistry, 2012
    Co-Authors: Gabriella Fogassy, Nicolas Thegarid, Yves Schuurman, Claude Mirodatos
    Abstract:

    A promising alternative to the first generation of bio-fuels is to produce mixed bio- and fossil fuels by Co-Processing mixtures of biomass pyrolysis oil with crude oil fractions obtained from distillation in a conventional oil refinery. This was demonstrated to be technically feasible for fluid catalytic cracking (FCC), which is the main refinery process for producing gasoline. However, Co-Processing leads to more coke formation and to a more aromatic gasoline fraction. A detailed understanding is necessary on how the oxygenated moieties effect the reaction mechanism to further improve the process/catalysts. Moreover, for technical and marketing reasons, it is absolutely required to accurately determine the proportion of renewable molecules in the commercialized products. The carbon-14 method (also called radiocarbon or 14C) has been used as the most accurate and powerful method to discriminate fossil carbon from bio-carbon, since fossil fuel is virtually 14C-free, while biofuel contains the present-day “natural” amount of 14C. This technique has shown that not all FCC products share bio-carbon statistically. The coke formed during a FCC cycle and to a lesser extent the gases are found richer in 14C than gasoline. This result gives valuable information on the Co-Processing mechanism, supporting that the bio-oil oxygenated molecules are processed more easily at the expenses of the crude oil hydrocarbons, favouring the bio-coke and the bio-light gases production.

  • From biomass to bio-gasoline by FCC Co-Processing: effect of feed composition and catalyst structure on product quality
    Energy and Environmental Science, 2011
    Co-Authors: Gabriella Fogassy, Nicolas Thegarid, Yves Schuurman, Claude Mirodatos
    Abstract:

    Due to a worldwide demand for biofuels, a need has emerged to develop new processes. Co-Processing of bio-oils in refinery units is a promising alternative, especially by Fluid Catalytic Cracking (FCC). In order to promote biofuel production by Co-Processing a detailed mechanistic study is required based on comparison with pure vacuum gasoil (VGO) processing. Three different porous materials containing micropores and/or mesopores were tested (FCC, HY and HZSM-5). The Co-Processing of hydrodeoxygenated pyrolysis oil (HDO-oil) with VGO in a lab test FCC unit leads to lower product formation rates than the processing of VGO alone, except for the coke formation and the formation of more unsaturated components (essentially aromatics). The data for both VGO cracking and Co-Processing follow the published trends with acid site density. These results are explained by the restricted access of the oxygenated molecules into the zeolite pores and coke formation on the outside surface leading to pore blocking. Another key mechanistic feature, explaining the observed effects of Co-Processing on the product quality, is the competition for the zeolite acid sites between the cracking route and the deoxygenation of the oxygenated components on the outer surface.

Gabriella Fogassy - One of the best experts on this subject based on the ideXlab platform.

  • second generation biofuels by co processing catalytic pyrolysis oil in fcc units
    Applied Catalysis B-environmental, 2014
    Co-Authors: Nicolas Thegarid, Gabriella Fogassy, Yves Schuurman, Claude Mirodatos, Stylianos D Stefanidis, E F Iliopoulou, Konstantinos G Kalogiannis, A A Lappas
    Abstract:

    Abstract Previous research showed that hydrodeoxygenated (HDO) pyrolysis-oils could successfully be co-processed with vacuum gasoil (VGO) in a labscale fluid catalytic cracking (FCC) unit to bio-fuels. Typically the hydrodeoxygenation step takes place at ∼300 °C under 200–300 bar of hydrogen. Eliminating or replacing this step by a less energy demanding upgrading step would largely benefit the FCC Co-Processing of pyrolysis oils to bio-fuels. In this paper a bio-oil that has been produced by catalytic pyrolysis (catalytic pyrolysis oil or CPO) is used directly, without further upgrading, in catalytic cracking Co-Processing mode with VGO. The results are compared to the Co-Processing of upgraded (via HDO) thermal pyrolysis oil. Though small but significant differences in the product distribution and quality have been observed between the Co-Processing of either HDO or CPO, they could be corrected by further catalyst development (pyrolysis and/or FCC), which would eliminate the need for an up-stream hydrodeoxygenation step. Moreover, the organic yield of the catalytic pyrolysis route is estimated at approximately 30 wt.% compared to an overall yield for the thermal pyrolysis followed by a hydrodeoxygenation step of 24 wt.%.

  • Second-generation biofuels by Co-Processing catalytic pyrolysis oil in FCC units
    Applied Catalysis B: Environmental, 2014
    Co-Authors: Nicolas Thegarid, Gabriella Fogassy, Yves Schuurman, Claude Mirodatos, Stylianos D Stefanidis, E F Iliopoulou, Konstantinos G Kalogiannis, A A Lappas
    Abstract:

    Previous research showed that hydrodeoxygenated (HDO) pyrolysis-oils could successfully be co-processed with vacuum gasoil (VGO) in a labscale fluid catalytic cracking (FCC) unit to bio-fuels. Typically the hydrodeoxygenation step takes place at similar to 300 degrees C under 200-300 bar of hydrogen. Eliminating or replacing this step by a less energy demanding upgrading step would largely benefit the FCC Co-Processing of pyrolysis oils to bio-fuels. In this paper a bio-oil that has been produced by catalytic pyrolysis (catalytic pyrolysis oil or CPO) is used directly, without further upgrading, in catalytic cracking Co-Processing mode with VGO. The results are compared to the Co-Processing of upgraded (via HDO) thermal pyrolysis oil. Though small but significant differences in the product distribution and quality have been observed between the Co-Processing of either HDO or CPO, they could be corrected by further catalyst development (pyrolysis and/or FCC), which would eliminate the need for an up-stream hydrodeoxygenation step. Moreover, the organic yield of the catalytic pyrolysis route is estimated at approximately 30 wt.% compared to an overall yield for the thermal pyrolysis followed by a hydrodeoxygenation step of 24 wt.%. (C) 2013 Elsevier B.V. All rights reserved.

  • the fate of bio carbon in fcc co processing products
    Green Chemistry, 2012
    Co-Authors: Gabriella Fogassy, Nicolas Thegarid, Yves Schuurman, Claude Mirodatos
    Abstract:

    A promising alternative to the first generation of bio-fuels is to produce mixed bio- and fossil fuels by Co-Processing mixtures of biomass pyrolysis oil with crude oil fractions obtained from distillation in a conventional oil refinery. This was demonstrated to be technically feasible for fluid catalytic cracking (FCC), which is the main refinery process for producing gasoline. However, Co-Processing leads to more coke formation and to a more aromatic gasoline fraction. A detailed understanding is necessary on how the oxygenated moieties effect the reaction mechanism to further improve the process/catalysts. Moreover, for technical and marketing reasons, it is absolutely required to accurately determine the proportion of renewable molecules in the commercialized products. The carbon-14 method (also called radiocarbon or 14C) has been used as the most accurate and powerful method to discriminate fossil carbon from bio-carbon, since fossil fuel is virtually 14C-free, while biofuel contains the present-day “natural” amount of 14C. This technique has shown that not all FCC products share bio-carbon statistically. The coke formed during a FCC cycle and to a lesser extent the gases are found richer in 14C than gasoline. This result gives valuable information on the Co-Processing mechanism, supporting that the bio-oil oxygenated molecules are processed more easily at the expenses of the crude oil hydrocarbons, favouring the bio-coke and the bio-light gases production.

  • From biomass to bio-gasoline by FCC Co-Processing: effect of feed composition and catalyst structure on product quality
    Energy and Environmental Science, 2011
    Co-Authors: Gabriella Fogassy, Nicolas Thegarid, Yves Schuurman, Claude Mirodatos
    Abstract:

    Due to a worldwide demand for biofuels, a need has emerged to develop new processes. Co-Processing of bio-oils in refinery units is a promising alternative, especially by Fluid Catalytic Cracking (FCC). In order to promote biofuel production by Co-Processing a detailed mechanistic study is required based on comparison with pure vacuum gasoil (VGO) processing. Three different porous materials containing micropores and/or mesopores were tested (FCC, HY and HZSM-5). The Co-Processing of hydrodeoxygenated pyrolysis oil (HDO-oil) with VGO in a lab test FCC unit leads to lower product formation rates than the processing of VGO alone, except for the coke formation and the formation of more unsaturated components (essentially aromatics). The data for both VGO cracking and Co-Processing follow the published trends with acid site density. These results are explained by the restricted access of the oxygenated molecules into the zeolite pores and coke formation on the outside surface leading to pore blocking. Another key mechanistic feature, explaining the observed effects of Co-Processing on the product quality, is the competition for the zeolite acid sites between the cracking route and the deoxygenation of the oxygenated components on the outer surface.

  • biomass derived feedstock co processing with vacuum gas oil for second generation fuel production in fcc units
    Applied Catalysis B-environmental, 2010
    Co-Authors: Gabriella Fogassy, Nicolas Thegarid, Yves Schuurman, Guy Toussaint, Andre C Van Veen, Claude Mirodatos
    Abstract:

    Hydrodeoxygenated pyrolysis-oils (HDO-oil) are considered promising renewable liquid energy carriers. As such, it cannot be applied in in-stationary combustion engines so more “upgrading” is required. A considerable alternative is to co-process HDO-oil along with vacuum gas oil (VGO) in a Fluid Catalytic Cracking unit (FCC). This study evaluates the impact of adding 20 wt.% HDO-oil to a conventional FCC feedstock. The VGO and bio-oil mixtures were co-injected into a fixed-bed reactor simulating FCC conditions using an equilibrated industrial FCC catalyst. Co-Processing of 20 wt.% HDO-oil with VGO gave comparable yields for the gasoline fraction to that of the pure VGO cracking. However, during Co-Processing oxygen removal from HDO-oil oxygenated components consumes hydrogen coming from the hydrocarbon feedstock. As a result the final product composition is poor in hydrogen and contains more coke, aromatics and olefins.

Nicolas Thegarid - One of the best experts on this subject based on the ideXlab platform.

  • second generation biofuels by co processing catalytic pyrolysis oil in fcc units
    Applied Catalysis B-environmental, 2014
    Co-Authors: Nicolas Thegarid, Gabriella Fogassy, Yves Schuurman, Claude Mirodatos, Stylianos D Stefanidis, E F Iliopoulou, Konstantinos G Kalogiannis, A A Lappas
    Abstract:

    Abstract Previous research showed that hydrodeoxygenated (HDO) pyrolysis-oils could successfully be co-processed with vacuum gasoil (VGO) in a labscale fluid catalytic cracking (FCC) unit to bio-fuels. Typically the hydrodeoxygenation step takes place at ∼300 °C under 200–300 bar of hydrogen. Eliminating or replacing this step by a less energy demanding upgrading step would largely benefit the FCC Co-Processing of pyrolysis oils to bio-fuels. In this paper a bio-oil that has been produced by catalytic pyrolysis (catalytic pyrolysis oil or CPO) is used directly, without further upgrading, in catalytic cracking Co-Processing mode with VGO. The results are compared to the Co-Processing of upgraded (via HDO) thermal pyrolysis oil. Though small but significant differences in the product distribution and quality have been observed between the Co-Processing of either HDO or CPO, they could be corrected by further catalyst development (pyrolysis and/or FCC), which would eliminate the need for an up-stream hydrodeoxygenation step. Moreover, the organic yield of the catalytic pyrolysis route is estimated at approximately 30 wt.% compared to an overall yield for the thermal pyrolysis followed by a hydrodeoxygenation step of 24 wt.%.

  • Second-generation biofuels by Co-Processing catalytic pyrolysis oil in FCC units
    Applied Catalysis B: Environmental, 2014
    Co-Authors: Nicolas Thegarid, Gabriella Fogassy, Yves Schuurman, Claude Mirodatos, Stylianos D Stefanidis, E F Iliopoulou, Konstantinos G Kalogiannis, A A Lappas
    Abstract:

    Previous research showed that hydrodeoxygenated (HDO) pyrolysis-oils could successfully be co-processed with vacuum gasoil (VGO) in a labscale fluid catalytic cracking (FCC) unit to bio-fuels. Typically the hydrodeoxygenation step takes place at similar to 300 degrees C under 200-300 bar of hydrogen. Eliminating or replacing this step by a less energy demanding upgrading step would largely benefit the FCC Co-Processing of pyrolysis oils to bio-fuels. In this paper a bio-oil that has been produced by catalytic pyrolysis (catalytic pyrolysis oil or CPO) is used directly, without further upgrading, in catalytic cracking Co-Processing mode with VGO. The results are compared to the Co-Processing of upgraded (via HDO) thermal pyrolysis oil. Though small but significant differences in the product distribution and quality have been observed between the Co-Processing of either HDO or CPO, they could be corrected by further catalyst development (pyrolysis and/or FCC), which would eliminate the need for an up-stream hydrodeoxygenation step. Moreover, the organic yield of the catalytic pyrolysis route is estimated at approximately 30 wt.% compared to an overall yield for the thermal pyrolysis followed by a hydrodeoxygenation step of 24 wt.%. (C) 2013 Elsevier B.V. All rights reserved.

  • the fate of bio carbon in fcc co processing products
    Green Chemistry, 2012
    Co-Authors: Gabriella Fogassy, Nicolas Thegarid, Yves Schuurman, Claude Mirodatos
    Abstract:

    A promising alternative to the first generation of bio-fuels is to produce mixed bio- and fossil fuels by Co-Processing mixtures of biomass pyrolysis oil with crude oil fractions obtained from distillation in a conventional oil refinery. This was demonstrated to be technically feasible for fluid catalytic cracking (FCC), which is the main refinery process for producing gasoline. However, Co-Processing leads to more coke formation and to a more aromatic gasoline fraction. A detailed understanding is necessary on how the oxygenated moieties effect the reaction mechanism to further improve the process/catalysts. Moreover, for technical and marketing reasons, it is absolutely required to accurately determine the proportion of renewable molecules in the commercialized products. The carbon-14 method (also called radiocarbon or 14C) has been used as the most accurate and powerful method to discriminate fossil carbon from bio-carbon, since fossil fuel is virtually 14C-free, while biofuel contains the present-day “natural” amount of 14C. This technique has shown that not all FCC products share bio-carbon statistically. The coke formed during a FCC cycle and to a lesser extent the gases are found richer in 14C than gasoline. This result gives valuable information on the Co-Processing mechanism, supporting that the bio-oil oxygenated molecules are processed more easily at the expenses of the crude oil hydrocarbons, favouring the bio-coke and the bio-light gases production.

  • From biomass to bio-gasoline by FCC Co-Processing: effect of feed composition and catalyst structure on product quality
    Energy and Environmental Science, 2011
    Co-Authors: Gabriella Fogassy, Nicolas Thegarid, Yves Schuurman, Claude Mirodatos
    Abstract:

    Due to a worldwide demand for biofuels, a need has emerged to develop new processes. Co-Processing of bio-oils in refinery units is a promising alternative, especially by Fluid Catalytic Cracking (FCC). In order to promote biofuel production by Co-Processing a detailed mechanistic study is required based on comparison with pure vacuum gasoil (VGO) processing. Three different porous materials containing micropores and/or mesopores were tested (FCC, HY and HZSM-5). The Co-Processing of hydrodeoxygenated pyrolysis oil (HDO-oil) with VGO in a lab test FCC unit leads to lower product formation rates than the processing of VGO alone, except for the coke formation and the formation of more unsaturated components (essentially aromatics). The data for both VGO cracking and Co-Processing follow the published trends with acid site density. These results are explained by the restricted access of the oxygenated molecules into the zeolite pores and coke formation on the outside surface leading to pore blocking. Another key mechanistic feature, explaining the observed effects of Co-Processing on the product quality, is the competition for the zeolite acid sites between the cracking route and the deoxygenation of the oxygenated components on the outer surface.

  • biomass derived feedstock co processing with vacuum gas oil for second generation fuel production in fcc units
    Applied Catalysis B-environmental, 2010
    Co-Authors: Gabriella Fogassy, Nicolas Thegarid, Yves Schuurman, Guy Toussaint, Andre C Van Veen, Claude Mirodatos
    Abstract:

    Hydrodeoxygenated pyrolysis-oils (HDO-oil) are considered promising renewable liquid energy carriers. As such, it cannot be applied in in-stationary combustion engines so more “upgrading” is required. A considerable alternative is to co-process HDO-oil along with vacuum gas oil (VGO) in a Fluid Catalytic Cracking unit (FCC). This study evaluates the impact of adding 20 wt.% HDO-oil to a conventional FCC feedstock. The VGO and bio-oil mixtures were co-injected into a fixed-bed reactor simulating FCC conditions using an equilibrated industrial FCC catalyst. Co-Processing of 20 wt.% HDO-oil with VGO gave comparable yields for the gasoline fraction to that of the pure VGO cracking. However, during Co-Processing oxygen removal from HDO-oil oxygenated components consumes hydrogen coming from the hydrocarbon feedstock. As a result the final product composition is poor in hydrogen and contains more coke, aromatics and olefins.

Yves Schuurman - One of the best experts on this subject based on the ideXlab platform.

  • FCC of upgraded pyrolysis liquid mixed crude oil distillates: combined strategies for improving bio-fuel yields and quality
    2017
    Co-Authors: Y. Chapelliere, Yves Schuurman, Claude Mirodatos, A. Tuel, S. Wellach, E. Jordan
    Abstract:

    In order to meet the EU’s renewable energy targets by 2020 (up to 10% share in all forms of transportation fuels), a realistic alternative to first generation bio-fuels is to produce hybrid bio/fossil fuels by co-refining biomass pyrolysis liquids (PL) with crude oil fractions in a conventional oil refinery. However, co-refining may lead to severe changes in products quality, such as a higher aromaticity and residual oxygenates in the hybrid fuels that are produced. For the case of co-FCC (fluid catalytic cracking), various strategies can be implemented to limit those impacts along this complex value chain ranging from bio-mass to bio-gasoline. A first strategy was tested to preserve the gasoline yield and quality by implementing a PL hydrotreating prior to Co-Processing, to lower their oxygen content. By following the changes in conversion, yields and gasoline composition (aromatics/olefins vs saturated alkanes) as a function of the bio-oils hydrotreating severity, measured in a Micro Activity Test (MAT) reactor, it was shown that a compromise could be reached between bio-oil upgrading severity and FCC products yields and quality (RON, PIONA analysis). An optimum in the gasoline yields and quality was found by adding 10 to 25 wt.% of a mildly deoxygenated bio-oil to a standard VGO, via a Co-Processing carried out on a commercial equilibrated FCC catalyst. A second strategy was to adapt the FCC catalysts to the presence of oxygenate molecules typical of the bio-feedstock still present in the upgraded pyrolytic liquids. To that end, Y zeolites, which are the main active component in FCC catalysts, were up-graded by creating a mesoporosity in addition to the microporosity to favor the diffusion of the large lignocellulosic fragments throughout the cracking catalysts, according various hierarchical post synthesis processes. The main effects of replacing progressively micro- by meso-porosity are i) to slightly increase naphta yields (Fig. 1), ii) to decrease coke formation at high conversion (Fig. 2), iii) to increase the unsaturated fraction in gaseous (C3-C5) (Fig. 3) and liquid products (not shown here), and iv) to decrease markedly the remaining oxygenated products in the liquid fraction (mainly alcohols, acids and phenolics, from 31PNMR measurements). These effects underline the positive role of creating a mesoporosity in hierarchical FCC catalysts, in line with cracking mechanistic features. The combined impact for these two strategies on co-FCC will be discussed as a guideline for minimizing the cost of bio-oils upgrading and thereof the hybrid transportation fuels, while maintaining their quality within the specification limits. Acknowledgements This study is supported by the “FASTCARD” EU FP7-NMP-2013 (GA n° 604277)

  • second generation biofuels by co processing catalytic pyrolysis oil in fcc units
    Applied Catalysis B-environmental, 2014
    Co-Authors: Nicolas Thegarid, Gabriella Fogassy, Yves Schuurman, Claude Mirodatos, Stylianos D Stefanidis, E F Iliopoulou, Konstantinos G Kalogiannis, A A Lappas
    Abstract:

    Abstract Previous research showed that hydrodeoxygenated (HDO) pyrolysis-oils could successfully be co-processed with vacuum gasoil (VGO) in a labscale fluid catalytic cracking (FCC) unit to bio-fuels. Typically the hydrodeoxygenation step takes place at ∼300 °C under 200–300 bar of hydrogen. Eliminating or replacing this step by a less energy demanding upgrading step would largely benefit the FCC Co-Processing of pyrolysis oils to bio-fuels. In this paper a bio-oil that has been produced by catalytic pyrolysis (catalytic pyrolysis oil or CPO) is used directly, without further upgrading, in catalytic cracking Co-Processing mode with VGO. The results are compared to the Co-Processing of upgraded (via HDO) thermal pyrolysis oil. Though small but significant differences in the product distribution and quality have been observed between the Co-Processing of either HDO or CPO, they could be corrected by further catalyst development (pyrolysis and/or FCC), which would eliminate the need for an up-stream hydrodeoxygenation step. Moreover, the organic yield of the catalytic pyrolysis route is estimated at approximately 30 wt.% compared to an overall yield for the thermal pyrolysis followed by a hydrodeoxygenation step of 24 wt.%.

  • Second-generation biofuels by Co-Processing catalytic pyrolysis oil in FCC units
    Applied Catalysis B: Environmental, 2014
    Co-Authors: Nicolas Thegarid, Gabriella Fogassy, Yves Schuurman, Claude Mirodatos, Stylianos D Stefanidis, E F Iliopoulou, Konstantinos G Kalogiannis, A A Lappas
    Abstract:

    Previous research showed that hydrodeoxygenated (HDO) pyrolysis-oils could successfully be co-processed with vacuum gasoil (VGO) in a labscale fluid catalytic cracking (FCC) unit to bio-fuels. Typically the hydrodeoxygenation step takes place at similar to 300 degrees C under 200-300 bar of hydrogen. Eliminating or replacing this step by a less energy demanding upgrading step would largely benefit the FCC Co-Processing of pyrolysis oils to bio-fuels. In this paper a bio-oil that has been produced by catalytic pyrolysis (catalytic pyrolysis oil or CPO) is used directly, without further upgrading, in catalytic cracking Co-Processing mode with VGO. The results are compared to the Co-Processing of upgraded (via HDO) thermal pyrolysis oil. Though small but significant differences in the product distribution and quality have been observed between the Co-Processing of either HDO or CPO, they could be corrected by further catalyst development (pyrolysis and/or FCC), which would eliminate the need for an up-stream hydrodeoxygenation step. Moreover, the organic yield of the catalytic pyrolysis route is estimated at approximately 30 wt.% compared to an overall yield for the thermal pyrolysis followed by a hydrodeoxygenation step of 24 wt.%. (C) 2013 Elsevier B.V. All rights reserved.

  • the fate of bio carbon in fcc co processing products
    Green Chemistry, 2012
    Co-Authors: Gabriella Fogassy, Nicolas Thegarid, Yves Schuurman, Claude Mirodatos
    Abstract:

    A promising alternative to the first generation of bio-fuels is to produce mixed bio- and fossil fuels by Co-Processing mixtures of biomass pyrolysis oil with crude oil fractions obtained from distillation in a conventional oil refinery. This was demonstrated to be technically feasible for fluid catalytic cracking (FCC), which is the main refinery process for producing gasoline. However, Co-Processing leads to more coke formation and to a more aromatic gasoline fraction. A detailed understanding is necessary on how the oxygenated moieties effect the reaction mechanism to further improve the process/catalysts. Moreover, for technical and marketing reasons, it is absolutely required to accurately determine the proportion of renewable molecules in the commercialized products. The carbon-14 method (also called radiocarbon or 14C) has been used as the most accurate and powerful method to discriminate fossil carbon from bio-carbon, since fossil fuel is virtually 14C-free, while biofuel contains the present-day “natural” amount of 14C. This technique has shown that not all FCC products share bio-carbon statistically. The coke formed during a FCC cycle and to a lesser extent the gases are found richer in 14C than gasoline. This result gives valuable information on the Co-Processing mechanism, supporting that the bio-oil oxygenated molecules are processed more easily at the expenses of the crude oil hydrocarbons, favouring the bio-coke and the bio-light gases production.

  • From biomass to bio-gasoline by FCC Co-Processing: effect of feed composition and catalyst structure on product quality
    Energy and Environmental Science, 2011
    Co-Authors: Gabriella Fogassy, Nicolas Thegarid, Yves Schuurman, Claude Mirodatos
    Abstract:

    Due to a worldwide demand for biofuels, a need has emerged to develop new processes. Co-Processing of bio-oils in refinery units is a promising alternative, especially by Fluid Catalytic Cracking (FCC). In order to promote biofuel production by Co-Processing a detailed mechanistic study is required based on comparison with pure vacuum gasoil (VGO) processing. Three different porous materials containing micropores and/or mesopores were tested (FCC, HY and HZSM-5). The Co-Processing of hydrodeoxygenated pyrolysis oil (HDO-oil) with VGO in a lab test FCC unit leads to lower product formation rates than the processing of VGO alone, except for the coke formation and the formation of more unsaturated components (essentially aromatics). The data for both VGO cracking and Co-Processing follow the published trends with acid site density. These results are explained by the restricted access of the oxygenated molecules into the zeolite pores and coke formation on the outside surface leading to pore blocking. Another key mechanistic feature, explaining the observed effects of Co-Processing on the product quality, is the competition for the zeolite acid sites between the cracking route and the deoxygenation of the oxygenated components on the outer surface.

A A Lappas - One of the best experts on this subject based on the ideXlab platform.

  • second generation biofuels by co processing catalytic pyrolysis oil in fcc units
    Applied Catalysis B-environmental, 2014
    Co-Authors: Nicolas Thegarid, Gabriella Fogassy, Yves Schuurman, Claude Mirodatos, Stylianos D Stefanidis, E F Iliopoulou, Konstantinos G Kalogiannis, A A Lappas
    Abstract:

    Abstract Previous research showed that hydrodeoxygenated (HDO) pyrolysis-oils could successfully be co-processed with vacuum gasoil (VGO) in a labscale fluid catalytic cracking (FCC) unit to bio-fuels. Typically the hydrodeoxygenation step takes place at ∼300 °C under 200–300 bar of hydrogen. Eliminating or replacing this step by a less energy demanding upgrading step would largely benefit the FCC Co-Processing of pyrolysis oils to bio-fuels. In this paper a bio-oil that has been produced by catalytic pyrolysis (catalytic pyrolysis oil or CPO) is used directly, without further upgrading, in catalytic cracking Co-Processing mode with VGO. The results are compared to the Co-Processing of upgraded (via HDO) thermal pyrolysis oil. Though small but significant differences in the product distribution and quality have been observed between the Co-Processing of either HDO or CPO, they could be corrected by further catalyst development (pyrolysis and/or FCC), which would eliminate the need for an up-stream hydrodeoxygenation step. Moreover, the organic yield of the catalytic pyrolysis route is estimated at approximately 30 wt.% compared to an overall yield for the thermal pyrolysis followed by a hydrodeoxygenation step of 24 wt.%.

  • Second-generation biofuels by Co-Processing catalytic pyrolysis oil in FCC units
    Applied Catalysis B: Environmental, 2014
    Co-Authors: Nicolas Thegarid, Gabriella Fogassy, Yves Schuurman, Claude Mirodatos, Stylianos D Stefanidis, E F Iliopoulou, Konstantinos G Kalogiannis, A A Lappas
    Abstract:

    Previous research showed that hydrodeoxygenated (HDO) pyrolysis-oils could successfully be co-processed with vacuum gasoil (VGO) in a labscale fluid catalytic cracking (FCC) unit to bio-fuels. Typically the hydrodeoxygenation step takes place at similar to 300 degrees C under 200-300 bar of hydrogen. Eliminating or replacing this step by a less energy demanding upgrading step would largely benefit the FCC Co-Processing of pyrolysis oils to bio-fuels. In this paper a bio-oil that has been produced by catalytic pyrolysis (catalytic pyrolysis oil or CPO) is used directly, without further upgrading, in catalytic cracking Co-Processing mode with VGO. The results are compared to the Co-Processing of upgraded (via HDO) thermal pyrolysis oil. Though small but significant differences in the product distribution and quality have been observed between the Co-Processing of either HDO or CPO, they could be corrected by further catalyst development (pyrolysis and/or FCC), which would eliminate the need for an up-stream hydrodeoxygenation step. Moreover, the organic yield of the catalytic pyrolysis route is estimated at approximately 30 wt.% compared to an overall yield for the thermal pyrolysis followed by a hydrodeoxygenation step of 24 wt.%. (C) 2013 Elsevier B.V. All rights reserved.

  • production of biofuels via co processing in conventional refining processes
    Catalysis Today, 2009
    Co-Authors: A A Lappas, Stella Bezergianni, I A Vasalos
    Abstract:

    Production of second-generation biofuels via gasification followed by Fischer–Tropsch synthesis is receiving increased attention due to the high-quality fuels produced. Although this process scheme produces fuel components compatible with conventional fossil fuels, the high-investment cost associated with its commercial application renders this option economically unfeasible. For this reason other process schemes are explored, primarily aiming to lower investment costs. Such options include coprocessing liquids from biomass flash pyrolysis in refining processes like fluid catalytic cracking (FCC) or in hydroprocessing. Vegetable oils could also by hydroprocessing with petroleum oils. In this paper small-scale pilot plant results will be presented from the following three process schemes aiming to the production of high-quality biofuels: (i) catalytic pyrolysis of biomass over FCC zeolitic catalysts at moderate temperatures. From this process the effect of catalyst on the yields of coke, gaseous and liquid products will be reported. (ii) Co-Processing gas oil mixed with hydrotreated biomass pyrolysis liquids. It will be shown that, depending on the concentration of biomass liquids, this option is technically viable for FCC units. (iii) Co-hydroprocessing vacuum gas oil (VGO) with sunflower oil to produce mid-distillates, mainly gasoline and diesel. For this option catalysts and process conditions will be discussed.