Biomass – Flare gas synergistic co-processing in the presence of carbon dioxide for the controlled production of syngas (H2:CO ~ 2 – 2.5)

Lalsare, Amoolya; Sivri, Ali; Egan, Ryan; Dumitrescu, Cosmin E.; Hu, Jianli

doi:10.1016/j.cej.2019.123783

Cited by 10 publications

(8 citation statements)

References 73 publications

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“…For the (101 ̅ 0) surface, oxygen prefers the long bridge and short bridge sites for Co and Ru, respectively, while on the (112 ̅ 0) surfaces the short bridge sites are favoured for both Co and Ru. In agreement with previous reports, bcc metals have a strong oxyphilic character [161][162][163][164], which may facilitate the direct cleavage of CꟷO bonds but will require elevated temperatures to release the oxygenated compounds. The different behaviour of these facets opens the possibility of nanoparticles engineering where the right ratio between desired facets may enhance the catalytic activity and selectivity towards specific products.…”

Section: Oxygen Adsorptionsupporting

confidence: 92%

Biomass hydrodeoxygenation catalysts innovation from atomistic activity predictors

Morteo-Flores

Engel

Roldán

2020

Phil. Trans. R. Soc. A.

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Circular economy emphasizes the idea of transforming products involving economic growth and improving the ecological system to reduce the negative consequences caused by the excessive use of raw materials. This can be achieved with the use of second-generation biomass that converts industrial and agricultural wastes into bulk chemicals. The use of catalytic processes is essential to achieve a viable upgrade of biofuels from the lignocellulosic biomass. We carried out density functional theory calculations to explore the relationship between 13 transition metals (TMs) properties, as catalysts, and their affinity for hydrogen and oxygen, as key species in the valourization of biomass. The relation of these parameters will define the trends of the hydrodeoxygenation (HDO) process on biomass-derived compounds. We found the hydrogen and oxygen adsorption energies in the most stable site have a linear relation with electronic properties of these metals that will rationalize the surface's ability to bind the biomass-derived compounds and break the C–O bonds. This will accelerate the catalyst innovation for low temperature and efficient HDO processes on biomass derivates, e.g. guaiacol and anisole, among others. Among the monometallic catalysts explored, the scaling relationship pointed out that Ni has a promising balance between hydrogen and oxygen affinities according to the d -band centre and d -band width models. The comparison of the calculated descriptors to the adsorption strength of guaiacol on the investigated surfaces indicates that the d -band properties alone are not best suited to describe the trend. Instead, we found that a linear combination of work function and d -band properties gives significantly better correlation. This article is part of a discussion meeting issue ‘Science to enable the circular economy’.

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Section: Oxygen Adsorptionsupporting

confidence: 92%

Biomass hydrodeoxygenation catalysts innovation from atomistic activity predictors

Morteo-Flores

Engel

Roldán

2020

Phil. Trans. R. Soc. A.

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“…Direct hydrogen transfer from methane coupled with hydrodeoxygenation (HDO) of biomass is a promising in situ technique to produce hydrogen-rich syngas from lignocellulosic biomass as reported earlier. Addition of low-concentration CO 2 possibly from flared gas allows for the controlled H 2 /CO ratio in syngas. , …”

Section: Introductionmentioning

confidence: 99%

“…Addition of low-concentration CO 2 possibly from flared gas allows for the controlled H 2 /CO ratio in syngas. 19,20 Catalyst development was performed using transition metals (TMs) viz. Fe, Ni, Mo, and Pd on a synthesized graphene nanosheet (GNS) support.…”

Section: ■ Introductionmentioning

confidence: 99%

Graphene-Supported Fe/Ni, β-Mo₂C Nanoparticles: Experimental and DFT Integrated Approach to Catalyst Development for Synergistic Hydrogen Production through Lignin-Rich Biomass Reforming and Reduced Shale Gas Flaring

et al. 2020

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Biomassflare gas synergistic coprocessing is a novel energy conversion technology that aims at harnessing an abundant renewable energy source: biomass and mitigate shale gas flaring. p-Cresol is used to represent lignin- and biomass-derived oxygenates for performing experimental and molecular reaction engineering of methane-assisted hydrodeoxygenation (HDO), hydrogenolysis reforming. The reaction pathway was also demonstrated on complex feedstocks like lignin and biomass, which contain a wide range of oxygenates in their composition. Novel in situ catalyst synthesis using a biomass precursor was achieved through pyrolysis to yield graphene nanosheet (GNS)-supported transition metal (TM) and Mo2C nanoparticles. Experimental work and density functional theory (DFT) modeling calculations were performed for methane-assisted p-cresol reforming using Fe, Ni, Mo2C, Fe–Mo2C, Ni–Mo2C, and Pd–Mo2C supported on GNS. Detailed mechanistic investigation of the methane–p-cresol synergistic reaction experimentally and through DFT-based molecular simulations helped ascertain the unique reaction pathway occurring on bifunctional (dual) active site-TM-doped β-Mo2C. Without TM doping, Mo2C is equally effective as Fe–Mo2C-GNS and Ni–Mo2C-GNS for CH4 dissociation and p-cresol HDO but presents a significantly higher barrier for H2 (1.7 eV vs 1.15, 1.13 eV) and CO (3.67 eV vs 2.87, 2.80 eV) gas-phase desorption. Dual active sites are required for hydrogen-rich syngas production through methane-assisted p-cresol reforming as validated by experiments, DFT calculations, and microkinetic modeling. Lignin and hardwood biomass both having a higher O/C weight ratio compared to p-cresol (0.46, 1.09 vs 0.19) were coprocessed with CH4 over Fe–Mo2C-GNS, Ni–Mo2C-GNS, and Pd–Mo2C-GNS catalysts. Fe-added Mo2C nanoparticles dispersed in the graphene support were found to be highly active for simultaneous CH4 activation and extensive HDO of p-cresol, lignin, and hardwood biomass. Higher HDO conversion and H2/CO ratios were obtained from CH4-assisted lignin/biomass reforming over Fe–Mo2C-GNS. Up to 99% hydrogen present in lignin could be valorized as syngas with a concentration of >65%.

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“…1−3 This biomass derived syngas usually has a H 2 /Co ratio around 2, which is suitable for Fischer−Tropsch synthesis (FTS) using cobalt-based catalysts. 1,2,4,5 The performance of cobalt-based catalysts in FTS is a function of the number, intrinsic activity, and stability of surface metal active sites. 6−9 Since FTS occurs on the surface of metallic cobalt, when cobalt reducibility is comparable, both the number and intrinsic activity of active sites are greatly determined by dispersion of cobalt species.…”

Section: Introductionmentioning

confidence: 99%

“…With the rapid depletion of petroleum reserves and ever demanding environmental requirements, it is necessary to develop new approaches to produce nonfossil-based fuels. One of the available approaches is the thermochemical processing of biomass into uniform intermediate products that can be biochemically converted to fuels and other chemicals, including gasification of the carbonaceous waste material into a volatile gaseous mixture called synthesis gas or syngas. − This biomass derived syngas usually has a H 2 /Co ratio around 2, which is suitable for Fischer–Tropsch synthesis (FTS) using cobalt-based catalysts. ,,, …”

Section: Introductionmentioning

confidence: 99%

Preparation of Highly Dispersed Nb₂O₅ Supported Cobalt-Based Catalysts for the Fischer–Tropsch Synthesis

Xiao

Han

Jing

et al. 2020

Ind. Eng. Chem. Res.

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In this work, niobia supported cobalt catalysts with both high cobalt dispersion and high cobalt loading (15 wt %) were prepared through the assistance of glow discharge plasma treatment, and their catalytic performance was tested in Fischer− Tropsch synthesis (FTS). Plasma treatment on support and especially on the decomposition of the catalyst precursor leads to a noticeable enhancement of cobalt dispersion. However, in addition to the cobalt dispersion improvement, plasma assisted decomposition of the cobalt precursor also led to the formation of CoNb 2 O 5 , which was inactive in FTS; moreover, the small cobalt particles underwent severe sintering during the reaction and caused significant and contineous deactivation. Plasma treatment on nobia could modify its porosity and hydrophilicity and generate surface functional groups; these features enabled an improved cobalt-niobia interaction and better cobalt dispersion on CoN(P)-C than on CoN-C. The enhanced FTS activity and best reaction stability on the CoN(P)-C catalyst were due to the possession of a suitable cobalt particle size and moderate cobalt-niobia interaction.

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Biomass – Flare gas synergistic co-processing in the presence of carbon dioxide for the controlled production of syngas (H2:CO ~ 2 – 2.5)

Cited by 10 publications

References 73 publications

Biomass hydrodeoxygenation catalysts innovation from atomistic activity predictors

Biomass hydrodeoxygenation catalysts innovation from atomistic activity predictors

Graphene-Supported Fe/Ni, β-Mo₂C Nanoparticles: Experimental and DFT Integrated Approach to Catalyst Development for Synergistic Hydrogen Production through Lignin-Rich Biomass Reforming and Reduced Shale Gas Flaring

Preparation of Highly Dispersed Nb₂O₅ Supported Cobalt-Based Catalysts for the Fischer–Tropsch Synthesis

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Biomass – Flare gas synergistic co-processing in the presence of carbon dioxide for the controlled production of syngas (H2:CO ~ 2 – 2.5)

Cited by 10 publications

References 73 publications

Biomass hydrodeoxygenation catalysts innovation from atomistic activity predictors

Biomass hydrodeoxygenation catalysts innovation from atomistic activity predictors

Graphene-Supported Fe/Ni, β-Mo2C Nanoparticles: Experimental and DFT Integrated Approach to Catalyst Development for Synergistic Hydrogen Production through Lignin-Rich Biomass Reforming and Reduced Shale Gas Flaring

Preparation of Highly Dispersed Nb2O5 Supported Cobalt-Based Catalysts for the Fischer–Tropsch Synthesis

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Graphene-Supported Fe/Ni, β-Mo₂C Nanoparticles: Experimental and DFT Integrated Approach to Catalyst Development for Synergistic Hydrogen Production through Lignin-Rich Biomass Reforming and Reduced Shale Gas Flaring

Preparation of Highly Dispersed Nb₂O₅ Supported Cobalt-Based Catalysts for the Fischer–Tropsch Synthesis