Low‐Temperature Reductive Aminolysis of Carbohydrates to Diamines and Aminoalcohols by Heterogeneous Catalysis

Pelckmans, Michiel; Vermandel, Walter; Waes, Frederik Van; Moonen, Kristof; Sels, Bert F.

doi:10.1002/ange.201708216

Cited by 16 publications

(18 citation statements)

References 33 publications

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“…One option is to apply the thermal pyrolysis of dextrose (glucose) which has been shown to give yields in excess of 70 mol % of glycolaldehyde . The resulting glycolaldehyde can in turn be converted to MEA by catalytic amination with yields of up to 90 mol %. − The integration of these two steps with the continuous MEA-to-taurine process described herein would provide the first complete biobased manufacturing process for taurine…”

Section: Further Innovation Opportunitiesmentioning

confidence: 99%

Continuous Process for the Production of Taurine from Monoethanolamine

Ma¹,

Butler²,

Milligan³

et al. 2020

Ind. Eng. Chem. Res.

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Taurine, 2-aminoethane-1-sulfonic acid, is a commercial amino acid manufactured from either ethylene oxide or monoethanolamine (MEA). Taurine is a valuable nutritional additive that is widely used in the production of energy drinks, pet food, nutritional supplements, and infant formula. The industrial production of taurine from MEA is a two-step batch process in which the first step is the reaction of MEA with sulfuric acid to produce the ester 2-aminoethyl hydrogen sulfate (AES) and the second step is the reaction of AES with a sulfite reagent. This report summarizes the results of a study of the fundamental chemistry for this two-step MEA-based chemical route to taurine as well as the application of this fundamental understanding to a process design for a scalable and cost-advantaged continuous process that is capable of commercial-scale production of taurine on a multikiloton scale. In order to maximize taurine yields, the water formed during the first esterification step must be effectively removed to avoid equilibrium limitations on the conversions of MEA and sulfuric acid to form the solid AES intermediate product. For the second AES sulfonation step in aqueous medium, we found that operation above 100 °C under a moderate pressure of an inert gas resulted in significantly higher taurine yields (>80 mol %) compared to those reported in current commercial production technology (typically 55–65 mol %).

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Section: Further Innovation Opportunitiesmentioning

confidence: 99%

Continuous Process for the Production of Taurine from Monoethanolamine

Ma¹,

Butler²,

Milligan³

et al. 2020

Ind. Eng. Chem. Res.

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“…It is commonly postulated that the amination of alcohols occurs via a “hydrogen borrowing” mechanism where a carbonyl compound is formed as an intermediate which is then converted into the imine and subsequently reduced to the amine. , Therefore, it seems to be attractive to start with a carbonyl compound and employ a reducing agent to produce alcohols. , One example is the production of ethanolamine from cellulose in a two-step process with a yield above 10% using hydrogen gas as reducing agent and a heterogeneous ruthenium catalyst for the reductive amination . Inspired by the naturally occurring aldolase enzyme, the direct reductive aminolysis of glucose toward several short-chained amines with carbon yields up to 87% have been achieved. , Likewise, the amination of isomannide, a renewable sugar-derivative, in water using a heterogeneous ruthenium catalyst has been demonstrated. This process can be extended to the conversion of other biogenic alcohols such as ethanol or hexane-1,6-diol …”

Section: O-containing Chemicalsmentioning

confidence: 99%

“…152 Inspired by the naturally occurring aldolase enzyme, the direct reductive aminolysis of glucose toward several short-chained amines with carbon yields up to 87% have been achieved. 153,154 Likewise, the amination of isomannide, a renewable sugar-derivative, in water using a heterogeneous ruthenium catalyst has been demonstrated. This process can be extended to the conversion of other biogenic alcohols such as ethanol or hexane-1,6-diol.…”

Section: ■ O-containing Chemicalsmentioning

confidence: 99%

Sustainable Routes for the Synthesis of Renewable Heteroatom-Containing Chemicals

Hülsey

Yang

Yan

2018

ACS Sustainable Chem. Eng.

152

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One of the biggest discrepancies between the structure of many utilized chemicals and petrochemicals is the ubiquity of heteroatoms in the former and the lack thereof in the latter. Many commodity chemicals and almost all specialty chemicals and pharmaceuticals contain one or more heteroatoms, but introducing functionalities containing oxygen, nitrogen, sulfur or phosphorus into crude oil-derived chemicals is often a very energy- and resource-intensive endeavor. This and the inevitable depletion of fossil resources in the not too distant future are the main reasons for the development of sustainable ways to produce compounds bearing heteroatoms. Synthesis of oxygen-containing compounds from renewable resources such as starch, cellulose and hemicellulose is already well-known, and the production of phenolic compounds from lignin is garnering significant attention recently. In the meantime, there is a surge in the valorization of chitin from waste crustacean and insect shells for the production of various nitrogen-containing compounds. Much less explored is the valorization of sulfur- and phosphorus-containing biomass components, although they find some high market value applications. Catalysis plays a central role to enable the conversion of biomass into value-added products with high activity and selectivity. Further developments made by chemical engineers and process technologists will be required to make those processes economically feasible and competitive with current synthetic schemes from fossil resources. This perspective highlights the most recent advances and the upcoming challenges in the development of renewable and sustainable routes toward heteroatom-containing chemicals.

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“…Several methods such as Strecker synthesis 6 have long been established, however, highly toxic cyanides and non-renewable aldehydes are used as substrates preventing their large-scale application 7 , 8 . The chemical routes to transform renewable organic carbon feedstocks and cheap, abundant NH 3 into amino acids 9 , 10 , and other relevant nitrogen-containing chemicals 11 – 16 in an energy-saving manner are highly desirable. For example, an exciting progress has recently been reported on the sustainable synthesis of glycine and alanine by catalytic fixation of N 2 and CO 2 17 .…”

Section: Introductionmentioning

confidence: 99%

Visible-light-driven amino acids production from biomass-based feedstocks over ultrathin CdS nanosheets

et al. 2020

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Chemical synthesis of amino acids from renewable sources is an alternative route to the current processes based on fermentation. Here, we report visible-light-driven amination of biomass-derived α-hydroxyl acids and glucose into amino acids using NH3 at 50 °C. Ultrathin CdS nanosheets are identified as an efficient and stable catalyst, exhibiting an order of magnitude higher activity towards alanine production from lactic acid compared to commercial CdS as well as CdS nanoobjects bearing other morphologies. Its unique catalytic property is attributed mainly to the preferential formation of oxygen-centered radicals to promote α-hydroxyl acids conversion to α-keto acids, and partially to the poor H2 evolution which is an undesired side reaction. Encouragingly, a number of amino acids are prepared using the current protocol, and one-pot photocatalytic conversion of glucose to alanine is also achieved. This work offers an effective catalytic system for amino acid synthesis from biomass feedstocks under mild conditions.

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Low‐Temperature Reductive Aminolysis of Carbohydrates to Diamines and Aminoalcohols by Heterogeneous Catalysis

Cited by 16 publications

References 33 publications

Continuous Process for the Production of Taurine from Monoethanolamine

Continuous Process for the Production of Taurine from Monoethanolamine

Sustainable Routes for the Synthesis of Renewable Heteroatom-Containing Chemicals

Visible-light-driven amino acids production from biomass-based feedstocks over ultrathin CdS nanosheets

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