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Development of Catalysts for Green Diesel Production

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A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Biomass Catalysis".

Deadline for manuscript submissions: closed (31 January 2019) | Viewed by 20029

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Special Issue Editor

Prof. Dr. Christos Kordulis

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Department of Chemistry, University of Patras, GR-26504 Patras, Greece
Interests: heterogeneous catalysis; synthesis and characterization of porous materials; catalyst preparation; surface characterization; catalytic oil upgrading processes; environmental catalysis; photocatalysis; development of catalysts for biofuel production
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Special Issue Information

Dear Colleagues,

Modern material culture is primarily based on fossil fuels (coal, oil, natural gas), which are going to be exhausted over the next two centuries, while energy demands will increase continuously due to the increase of the Earth’s population and standards of living. At the same time, there are now very strong indications that global warming is accelerating, causing severe climate disturbances due to the ever-increasing carbon dioxide emissions caused by the burning of fossil fuels.

The scientific community is searching for solutions to the aforementioned problems, adopting a holistic approach to the dual—energy and climate—challenge with complementary use of renewable energy. The proposed solutions involve combined exploitation of renewable energy, like sun energy, wind energy, hydropower, ocean energy, geothermal energy, etc. These kinds of energy could be easily transformed into electricity and transferred by the existing grid to cover the major part of energy demands of households and industry. However, the restricted storage possibilities of electrical energy do not allow, at the moment, the complete use of this kind of energy in the transportation sector.

Existing transportation technology has been developed based on liquid fossil fuels (gasoline, kerosene and diesel); thus, renewable substitutes for these fuels can easily satisfy the relevant demands without substantial change concerning this technology.

Renewable liquid fuels can be produced from biomass, which is easily found everywhere on the planet’s surface. Extensive research concerns the exploitation of lignocellulosic biomass (especially that of residues) from which bio-oil can be produced. Bio-oil, an oxygen-rich liquid with a very complex composition, needs substantial deoxygenation before it can be transformed into green fuels.

Animal fats and vegetable oils constitute a simpler kind of biomass that can be harnessed for the production of green jet/diesel fuel. However, some researchers have raised concerns regarding the potential interference in nutritional consumption if virgin triglyceride biomass was employed in the green jet/diesel fuel production.

In view of this, there is continuous research into the exploitation of non-edible oil as a feedstock for green jet/diesel fuel. A few of the proven, non-edible oils that can be used as jet/diesel feedstocks are Jatropha oil; fatty acid distillates; microalgae oil; and waste cooking oil. The latter three are preferable because they do not need arable terrenes for their cultivation.

The development of catalysts for green diesel production via deoxygenation of the aforementioned oils has attracted a great deal of interest. This Special Issue of Catalysts aspires to collect and present the newest achievements in this field.

Prof. Dr. Christos Kordulis
Guest Editor

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Keywords

bio-oil upgrading
green diesel
catalyst development
deoxygenation
hydrotreatment
non-edible oil
renewable fuel
renewable diesel

Published Papers (4 papers)

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Research

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16 pages, 3985 KiB

Open AccessArticle

Hydrogenation of Bio-Oil Model Compounds over Raney-Ni at Ambient Pressure

by Bogdan Shumeiko, Klaus Schlackl and David Kubička

Catalysts 2019, 9(3), 268; https://doi.org/10.3390/catal9030268 - 15 Mar 2019

Cited by 4 | Viewed by 3488

Abstract

Lignocellulosic biofuels are the most promising sustainable fuels that can be added to the crude oil pool to refill the dwindling fossil resources. In this work, we tested a Raney-Ni catalyst for the hydrogenation of four bio-oil model compounds and their binary mixtures to assess their reactivity under mild conditions suitable for bio-oil stabilization preceding green diesel production from lignocellulosic biomass. The hydrogenation experiments were performed at ambient hydrogen pressure at temperatures in the range 30–70 °C. Raney-Ni was found to hydrogenate all investigated model compounds efficiently; both carbonyl groups and double bonds were saturated. In addition, it was also active in the demethoxylation of guaiacol. When studying the binary mixtures, furfuryl alcohol was found to significantly inhibit the hydrogenation of the other model compounds (guaiacol and methyl isobutyl ketone) due to their very strong adsorption. Full article

(This article belongs to the Special Issue Development of Catalysts for Green Diesel Production)

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19 pages, 5056 KiB

Open AccessArticle

Developing Nickel–Zirconia Co-Precipitated Catalysts for Production of Green Diesel

by Georgios Zafeiropoulos, Nikolaos Nikolopoulos, Eleana Kordouli, Labrini Sygellou, Kyriakos Bourikas, Christos Kordulis and Alexis Lycourghiotis

Catalysts 2019, 9(3), 210; https://doi.org/10.3390/catal9030210 - 26 Feb 2019

Cited by 31 | Viewed by 3297

Abstract

The transformation of sunflower oil (SO) and waste cooking oil (WCO) into green diesel over co-precipitated nickel–zirconia catalysts was studied. Two series of catalysts were prepared. The first series included catalysts with various Ni loadings prepared using zirconium oxy-chloride, whereas the second series included catalysts with 60–80 wt % Ni loading prepared using zirconium oxy-nitrate as zirconium source. The catalysts were characterized and evaluated in the transformation of SO into green diesel. The best catalysts were also evaluated for green diesel production using waste cooking oil. The catalysts performance for green diesel production is mainly governed by the Ni surface exposed, their acidity, and the reducibility of the ZrO₂. These characteristics depend on the preparation method and the Zr salt used. The presence of chlorine in the catalysts drawn from the zirconium oxy-chloride results to catalysts with relatively low Ni surface, high acidity and hardly reduced ZrO₂ phase. These characteristics lead to relatively low activity for green diesel production, whereas they favor high yields of wax esters. Ni-ZrO₂ catalysts with Ni loading in the range 60–80 wt %, prepared by urea hydrothermal co-precipitation method using zirconium oxy-nitrate as ZrO₂ precursor salt exhibited higher Ni surface, moderate acidity, and higher reducibility of ZrO₂ phase. The latter catalysts were proved to be very promising for green diesel production. Full article

(This article belongs to the Special Issue Development of Catalysts for Green Diesel Production)

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20 pages, 7432 KiB

Open AccessArticle

Effect of Pt Promotion on the Ni-Catalyzed Deoxygenation of Tristearin to Fuel-Like Hydrocarbons

by Ryan Loe, Kelsey Huff, Morgan Walli, Tonya Morgan, Dali Qian, Robert Pace, Yang Song, Mark Isaacs, Eduardo Santillan-Jimenez and Mark Crocker

Catalysts 2019, 9(2), 200; https://doi.org/10.3390/catal9020200 - 22 Feb 2019

Cited by 15 | Viewed by 4383

Abstract

Pt represents an effective promoter of supported Ni catalysts in the transformation of tristearin to green diesel via decarbonylation/decarboxylation (deCO_x), conversion increasing from 2% over 20% Ni/Al₂O₃ to 100% over 20% Ni-0.5% Pt/Al₂O₃ at 260 °C. Catalyst characterization reveals that the superior activity of Ni-Pt relative to Ni-only catalysts is not a result of Ni particle size effects or surface area differences, but rather stems from several other phenomena, including the improved reducibility of NiO when Pt is present. Indeed, the addition of a small amount of Pt to the supported Ni catalyst dramatically increases the amount of reduced surface metal sites, which are believed to be the active sites for deCO_x reactions. Further, Pt addition curbs the adsorption of CO on the catalyst surface, which decreases catalyst poisoning by any CO evolved via decarbonylation, making additional active sites available for deoxygenation reactions and/or preventing catalyst coking. Specifically, Pt addition weakens the Ni-CO bond, lowering the binding strength of CO on surface Ni sites. Finally, analysis of the spent catalysts recovered from deCO_x experiments confirms that the beneficial effect of Pt on catalyst performance can be partially explained by decreased coking and fouling. Full article

(This article belongs to the Special Issue Development of Catalysts for Green Diesel Production)

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Review

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27 pages, 2101 KiB

Open AccessEditor’s ChoiceReview

Transition Metal Phosphides for the Catalytic Hydrodeoxygenation of Waste Oils into Green Diesel

by M. Consuelo Alvarez-Galvan, Jose M. Campos-Martin and Jose L. G. Fierro

Catalysts 2019, 9(3), 293; https://doi.org/10.3390/catal9030293 - 22 Mar 2019

Cited by 71 | Viewed by 8147

Abstract

Recently, catalysts based on transition metal phosphides (TMPs) have attracted increasing interest for their use in hydrodeoxygenation (HDO) processes destined to synthesize biofuels (green or renewable diesel) from waste vegetable oils and fats (known as hydrotreated vegetable oils (HVO)), or from bio-oils. This fossil-free diesel product is produced completely from renewable raw materials with exceptional quality. These efficient HDO catalysts present electronic properties similar to noble metals, are cost-efficient, and are more stable and resistant to the presence of water than other classical catalytic formulations used for hydrotreatment reactions based on transition metal sulfides, but they do not require the continuous supply of a sulfide source. TMPs develop a bifunctional character (metallic and acidic) and present tunable catalytic properties related to the metal type, phosphorous-metal ratio, support nature, texture properties, and so on. Here, the recent progress in TMP-based catalysts for HDO of waste oils is reviewed. First, the use of TMPs in catalysis is addressed; then, the general aspects of green diesel (from bio-oils or from waste vegetable oils and fats) production by HDO of nonedible oil compounds are presented; and, finally, we attempt to describe the main advances in the development of catalysts based on TMPs for HDO, with an emphasis on the influence of the nature of active phases and effects of phosphorous, promoters, and preparation methods on reactivity. Full article

(This article belongs to the Special Issue Development of Catalysts for Green Diesel Production)

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