Uncovering the active sites and demonstrating stable catalyst for the cost-effective conversion of ethanol to 1-butanol

Guo, Mond F.; Gray, Michel J.; Job, Heather; Alvarez-Vasco, Carlos; Subramaniam, Senthil; Zhang, Xiao; Kovařík, Libor; Vijayakumar, M.; Phillips, Steven D.; Ramasamy, Karthikeyan

doi:10.1039/d1gc01979a

Cited by 13 publications

(12 citation statements)

References 61 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Figure 4 depicts three biorefinery models for fuel and chemical production through butanol production from ethanol. For flowsheet A‐nBuOH and flowsheet C‐nBuOH, either all or a fraction of the ethanol is converted to butanol co‐product via a Guerbet process 10–13 . After butanol recovery, the remaining ethanol is converted to olefins that are oligomerized using a two‐step process 13 and then hydrogenated to hydrocarbon fuels.…”

Section: Methodology and Process Descriptionmentioning

confidence: 99%

“…For flowsheet A-nBuOH and flowsheet C-nBuOH, either all or a fraction of the ethanol is converted to butanol co-product via a Guerbet process. [10][11][12][13] After butanol recovery, the remaining ethanol is converted to olefins that are oligomerized using a two-step process 13 and then hydrogenated to hydrocarbon fuels. For flowsheet B-nBuOH, all the ethanol is converted to butanol co-product while hydrocarbon fuel is produced from the bioconversion residuals using an HTL process.…”

Section: Conversion Routes Of Ethanol To Produce Hydrocarbon Fuels An...mentioning

confidence: 99%

See 1 more Smart Citation

Techno‐economic analysis of cellulosic ethanol conversion to fuel and chemicals

Phillips

Jones

Meyer

et al. 2022

Biofuels Bioprod Bioref

View full text Add to dashboard Cite

In this paper, we describe multiple scenarios to assess the techno-economic results of producing hydrocarbon fuels from corn stover-derived ethanol and the impact of co-producing highervalue, ethanol-derived n-butanol and 1,3-butadiene to improve economic feasibility. In our baseline process, the stover-derived lignin is burned for its energy content to raise process steam and electricity. We evaluated an alternative approach based on the same stover-to-ethanol process, but instead of burning residual lignin to produce heat and electricity, it was fed to a hydrothermal liquefaction process and converted into hydrocarbon fuel, while the ethanol from fermentation is used to make only butanol or butadiene. Our results indicate that the hydrothermal liquefaction pathways have significant cost advantages over the pathways that burn the lignin. For comparison purposes, two more scenarios were evaluated based on the assumption that ethanol was purchased at market prices and converted to butanol or butadiene exclusively. This comparison evaluates the economics for making higher-valued chemicals which, in the absence of incentives, would be the most profitable approaches in our study. The results for these evaluations indicated that the ethanol-to-butanol economics were generally favorable and achieved or exceeded the 10% internal rate of return target. The butadiene process had less favorable economic performance in some years when the market price for butadiene was less than the selling price needed to achieve the internal rate of return. Economic incentives for low-carbon chemicals and fuels were not considered in our analysis.

show abstract

Section: Methodology and Process Descriptionmentioning

confidence: 99%

Section: Conversion Routes Of Ethanol To Produce Hydrocarbon Fuels An...mentioning

confidence: 99%

Techno‐economic analysis of cellulosic ethanol conversion to fuel and chemicals

Phillips

Jones

Meyer

et al. 2022

Biofuels Bioprod Bioref

View full text Add to dashboard Cite

show abstract

“…Acetaldehyde was observed to be selective on Cu/ t -ZrO 2 , whereas Cu/ m -ZrO 2 showed a high selectivity for ethyl acetate, which was described by the mobility of oxygen from zirconia to a copper site resulting in electron transfer between support and copper . Guo et al utilized single atom Cu 1+ sites on MgAl mixed oxide support to demonstrate a highly selective conversion of ethanol to higher alcohols such as butanol . At low loading of copper on MgAl oxide support, a high dispersion of single atom Cu 1+ sites is achievable, which showed high stability up to 150 h TOS run while maintaining the selectivity for butanol .…”

Section: Catalysts For Ethanol Dehydrogenation and Decompositionmentioning

confidence: 99%

“…Guo et al utilized single atom Cu 1+ sites on MgAl mixed oxide support to demonstrate a highly selective conversion of ethanol to higher alcohols such as butanol . At low loading of copper on MgAl oxide support, a high dispersion of single atom Cu 1+ sites is achievable, which showed high stability up to 150 h TOS run while maintaining the selectivity for butanol . Pinzón et al developed a calcium based bifunctional acid–base catalyst for ethanol condensation to n -butanol and conducted in situ DRIFT-MS studies to understand the mechanism on the acid–base sites .…”

Section: Catalysts For Ethanol Dehydrogenation and Decompositionmentioning

confidence: 99%

Ethanol Decomposition and Dehydrogenation for Hydrogen Production: A Review of Heterogeneous Catalysts

Kumar

2021

Ind. Eng. Chem. Res.

View full text Add to dashboard Cite

Biowaste derived ethanol is an important feedstock for carbon neutral hydrogen production. It is liquid at atmospheric conditions, has a high hydrogen to carbon ratio, and it can be generated from biomass, lignocellulosic wastes, and sewage sludge, offering opportunities for converting waste to hydrogen as an alternative to fossil fuels-based sources of hydrogen. A large-scale application of bioethanol for hydrogen production has the potential to considerably reduce CO2 emissions. Recent reviews on ethanol reforming for hydrogen production show a growth in research interest in this topic, although primarily focused on ethanol steam reforming (ESR) in which steam, in addition to ethanol, also acts as an additional source of hydrogen. Ethanol partial oxidation (POx) is another relatively well-studied route, which is exothermic in nature; however, hydrogen selectivity can be compromised due to the presence of oxygen leading to water formation. Ethanol decomposition and dehydrogenation (ED) are relatively less studied compared to the other two routes, possibly due to coke formation that often leads to catalyst deactivation. The past decade has seen an increasing number of papers on ED to exploit it for the production of aldehydes, acetates, and ethers, as well as various forms of carbon along with hydrogen. The goal of this article is to provide a review on the recent development in nonoxidative ethanol dehydrogenation and ethanol decomposition catalysis for hydrogen production. Catalytic studies over the past few decades have benefitted from the unprecedented growth in experimental techniques, particularly from in situ transmission electron microscopy (in situ TEM) and near ambient X-ray photoelectron spectroscopy (NA-XPS), allowing researchers to obtain dynamic structural information caused by reactant–catalyst interactions leading to greater insights based on more realistic information. A review incorporating the current status will allow us to better understand the structure–performance relationship, leading to the implementation of practical and realistic considerations for catalysts synthesis and reactor design for stable performance. The present review is an attempt to put together the recent progress, mainly in the past decade, on the catalysts for ethanol dehydrogenation, experimental conditions for effective extraction of hydrogen and targeted products, and metal–support interactions and their contribution in directing the reaction pathways. For the ease of reading and comprehension, the article is divided into subsections based on metals (transition metals and noble metals) and supports. The review concludes with a table listing the catalysts, synthesis method, reaction environments, and key findings for a quick and easy access to the critical systems assessed during the review process.

show abstract

“…However, the weak dehydrogenation/hydrogenation over Lewis acid/base sites restrains the ethanol valorization . Considering both perspectives, tailoring the acid–base catalysts by introducing transition metal species (such as Co, Ni, Cu, , Zn, and Pd) as dehydrogenation sites might improve the performance toward higher alcohols. Cu has been frequently chosen as a dehydrogenation catalyst for ethanol conversion. , Recently, Ramasamy and co-workers reported that Cu/Mg x Al y O achieved 75% 1-butanol and higher alcohol selectivity at 59% ethanol conversion .…”

Section: Introductionmentioning

confidence: 99%

Enhancing Ethanol Coupling to Produce Higher Alcohols by Tuning H₂ Partial Pressure over a Copper-Hydroxyapatite Catalyst

Zhou

et al. 2022

ACS Catal.

View full text Add to dashboard Cite

Catalytic upgrading of ethanol, as a platform molecule from biomass to higher alcohols (C4–12), is a low-carbon route for value-added chemical production. However, the products are generally obtained in low selectivity due to the uncontrollable reactivity of intermediates that cause a complex reaction network. In this study, we show that unsaturated intermediates of aldehydes can be rapidly hydrogenated by surface hydrogen species during the ethanol upgrading process, thereby greatly inhibiting the cyclization reaction of aldehydes. Specifically, the product distributions on the Cu-hydroxyapatite (Cu-HAP) catalyst shift stepwise to higher alcohols from aromatic oxygenates with the partial pressure of hydrogen increasing from 0 to 95 kPa. Kinetic measurements and in situ ethanol infrared results indicated that the intermediates during this process are acetaldehyde and 2-butenal. Combined with physical structure and chemical state analysis of the catalyst, we found that Cu sites catalyze the hydrogenation of the CC bond of 2-butenal under a hydrogen atmosphere. The C–C coupling of ethanol to higher alcohols over Cu-HAP follows the Guerbet mechanism. In comparison, on bare HAP, n-butanol is formed as a primary product even though little amount of acetaldehyde was detected, indicating that ethanol proceeds mainly in a direct coupling process to yield higher alcohols. This study introduces an efficient ethanol valorization approach that is enabled by subtle control of the intermediate conversion over the Cu-HAP catalyst by the hydrogen partial pressure.

show abstract

Uncovering the active sites and demonstrating stable catalyst for the cost-effective conversion of ethanol to 1-butanol

Abstract: The recent emergence of a robust renewable ethanol industry has provided a sustainable platform molecule toward the production of value-added chemicals and fuels; what is lacking now are viable conversion...

Cited by 13 publications

References 61 publications

Techno‐economic analysis of cellulosic ethanol conversion to fuel and chemicals

Techno‐economic analysis of cellulosic ethanol conversion to fuel and chemicals

Ethanol Decomposition and Dehydrogenation for Hydrogen Production: A Review of Heterogeneous Catalysts

Enhancing Ethanol Coupling to Produce Higher Alcohols by Tuning H₂ Partial Pressure over a Copper-Hydroxyapatite Catalyst

Contact Info

Product

Resources

About

Uncovering the active sites and demonstrating stable catalyst for the cost-effective conversion of ethanol to 1-butanol

Abstract: The recent emergence of a robust renewable ethanol industry has provided a sustainable platform molecule toward the production of value-added chemicals and fuels; what is lacking now are viable conversion...

Cited by 13 publications

References 61 publications

Techno‐economic analysis of cellulosic ethanol conversion to fuel and chemicals

Techno‐economic analysis of cellulosic ethanol conversion to fuel and chemicals

Ethanol Decomposition and Dehydrogenation for Hydrogen Production: A Review of Heterogeneous Catalysts

Enhancing Ethanol Coupling to Produce Higher Alcohols by Tuning H2 Partial Pressure over a Copper-Hydroxyapatite Catalyst

Contact Info

Product

Resources

About

Enhancing Ethanol Coupling to Produce Higher Alcohols by Tuning H₂ Partial Pressure over a Copper-Hydroxyapatite Catalyst