Amines have a bad guy reputation, in part because controversial compounds like cocaine, heroin, nicotine and mescaline are among the alkaloids that are, when you get down to it, a special class of amines.<\/p>\n
And if you find something that blows up with great destructive force, you\u2019ll find an amine in the mix (think, on the good side, automotive airbags, but you\u2019ll find high energy explosives used in military operations at the rough stuff end of the spectrum). For that reason, they\u2019re usually grouped with Yosemite Sam among the \u201cmeanest. roughest, toughest hombres that ever crossed the blood-brain barrier\u201d. Or something like that.<\/p>\n
Lately the amines, which in the simplest description are compounds with a bunch of nitrogen stuffed inside, have improved their reputation. For one, a number of Direct Air Capture technologies have been receiving big publicity as climate fighters for their CO2-scrubbing prowess. If you saw the film Apollo 13, you\u2019ll know how powerful and vital CO2 removal technology can be, and that\u2019s generally accomplished with amines.
\nAs Michiel Pelckmans wrote in 2017 in a PhD thesis on the catalytic production of bio-based amines and derivatives:<\/p>\n
Amines are\u2026building blocks of polymers, surfactants, pharmaceuticals and agrochemicals, and they are used as CO2 absorbents or as catalysts, for instance for polyurethane synthesis. So far, industrial amines are produced from petrochemical resources\u2026Moreover, their synthesis procedures involve toxic, explosive and\/or expensive chemicals and intermediates, therefore not in line with the green chemistry principles of tomorrows chemical industry.\u201d<\/p>\n
Biobased alternatives
\nPelckmans provided this guide, noting:<\/p>\n
\u201cvarious bio-based amines (blue box) that are obtained via specific (heterogeneous) catalytic transformations of the renewable platform molecules (orange boxes). These platform compounds are in turn produced through (catalytic) transformation of the different types of biomass (green boxes).\u201d<\/p>\n
Catalyst advances
\nBeyond platinum, there\u2019s ruthenium, which wouldn\u2019t be exactly cheap. Nonetheless, researchers reported in Chemical Science last year:<\/p>\n
Specific flat-shaped pristine fcc ruthenium nanoparticles having a large fraction of atomically active facets exposed on their flat surfaces have been developed that act as a highly selective and reusable heterogeneous catalyst for the production of various primary amines at exceedingly high reaction rates by the low temperature reductive amination of carbonyl compounds.\u201d<\/p>\n
Carbonyl compounds include a whole bunch of stuff, including aldehydes, carboxylic acids, amides \u2014 all highly suitable to the world of biobased development. Think formic acid, acetic acid, butyric acid, the caprylic acid found in coconuts, the capric and palmitic oils found in palm. You can find a lot of these compounds made, biobased, by Arkema under the Oleris brand, and more on that here.<\/p>\n
Who makes them thar amines?<\/p>\n
When you ask yourself \u201cwho is the world leader in [pick your chemical of choice], the safe answer is usually \u201cBASF\u201d. And when it comes to amines, you never heard of so many brans in your life ending in \u201cOR\u201d \u201cAR\u201d UR\u201d \u201cOL\u201d or \u201cIL\u201d until you\u2019ve leafed through BASF\u2019s amines and ethanolamines portfolio.<\/p>\n
As BASF advises, the uses are many: construction, gas treatment, surfactants for personal care, wood preservation, agrochemical production, wet strength resins, detergents, water softening, anti-corrosives. Well, you get the idea, a lot of stuff \u2014 and as we read above, not always made via pretty green processes or intermediates you could soak your hands in. There\u2019s a lot of BLAM! BLAM! in amines, or BLAMINE, if you will.<\/p>\n
The markets are small-ish but the margins delightful \u2014 perfect targets for small biobased operations looking for a way forward in the years before they achieve world-scale commercial-scale.<\/p>\n
Who are the kings and queens of the clean green amine gene scene?
\nLet\u2019s look into advances with inorganic catalysts and mighty microbes.<\/p>\n
Among this year\u2019s crop of research papers, we noted that researchers from the University of Bordeaux and the ArianeGroup highlighted:<\/p>\n
\u201cBio-based aromatic diamines from vanillin substrate were successfully synthesized and characterized. These amines, i.e., methylated divanillylamine (MDVA) and 3,4-dimethoxydianiline (DMAN), were then tested as curing agents for the design of bio-based epoxy thermosets. The epoxy thermosets obtained from these novel vanillin-based amines exhibited promising thermomechanical properties in terms of glass transition temperature and char residue.\u201d<\/p>\n
From Green Chemistry, let\u2019s highlight this one:<\/p>\n
New bio-based amine monomers derived from vanillin were prepared by the direct amination of an epoxy monomer with aqueous ammonia. These synthesized amines exhibited high reactivity due to the presence of secondary OH groups. Then these amines were added to epoxies to form thermosets by a cross-linking reaction.<\/p>\n
From a slightly older edition of the same journal, let\u2019s highlight this one:<\/p>\n
The production of amines from biomass is a growing field of interest. Particularly the amination of bio-based alcohols receives a lot of attention. In this review, we discuss recent progress in the development of efficient heterogeneous catalysts. The substrate scope for the production of bio-based amines is not limited to (hemi)cellulosic alcohols. Other platform chemicals that originate from different biomass fractions, such as lignin, oils, chitin and protein, are also suitable feedstock for the production of amines. This comprehensive review first provides an overview of the available bio-based feedstock candidates. The following section is devoted to the sustainable reaction routes that are available to carry out the desired amination reactions.<\/p>\n
And this evergreen review for the year prior, published in Chemical Reviews:<\/p>\n
In this review we present both fundamental and applied research on the synthesis of biobased primary and secondary amines with current available biobased resources. Their use is described as a building block for material chemistry. Hence, we first recall some background on the synthesis of amines, including the reactivity of amines.<\/p>\n
Who\u2019s working on it?
\nThe leader is, as noted above, BASF. And they\u2019re doubling down on traditional sources, As we reported in April, \u201cBASF will increase the production capacity of Alkylethanolamines (AEOA) by 20 percent at the BASF Verbund site in Ludwigshafen. After the start-up in 2020, BASF\u2019s global annual nameplate capacity of AEOA will be more than 110,000 metric tons per year at its production facilities in Ludwigshafen, Germany; Geismar, USA; and Nanjing, China.<\/p>\n
\u201cAs one of the world\u2019s leading suppliers of amines, we continue to support the fast-growing customer demand for products of our Alkylethanolamine portfolio by increasing our capacity. The demand is particularly high for high-performance products in the Water- and Gas Treatment industries\u201d, said Dr. Andrea Frenzel, President, BASF Intermediates Division.<\/p>\n
But others are in the mix, For example, Zymergen. We spotted a need for a polymer chemist a while back requiring \u201cexpertise in synthesizing amine-functional resins, polyols, epoxies, isocyanates, adhesion promotors, additives, and UV curable resins.\u201d<\/p>\n
Intermediates
\nAs this review notes:<\/p>\n
Acrylamides are produced by the treatment of 3-HPA with an amine\u2026polyacrylamide is not toxic and is used in various applications such as in water treatment, paper manufacture, mining, oil recovery, absorbents and as electrophoresis gels. Acrolein and acrylonitrile are two other industrially essential derivatives which are used in the synthesis of various polymers.<\/p>\n
Which makes 3-HP and 3-HPA and amines a couple of targets of interest. As the researchers note, \u201c3-HP and 3-HPA can be converted to various value-added chemicals such as acrolein, acrylic acid, acrylic acid esters and amides, 1,3-propanediol, malonic acid and 3-hydroxypropionic esters.\u201d One of the reasons that a famed DOE review of potential biobased targets had 3-HPA in the third position, though it has not been successfully pursued as a major commercial target.<\/p>\n
Though, we did report back in 2017 that \u201cthe National Renewable Energy Laboratory (NREL) established a novel catalytic method to produce renewable acrylonitrile using 3-hydroxypropionic acid (3-HP), which can be biologically produced from sugars. This hybrid biological-catalytic process offers an alternative to the conventional petrochemical production method and achieves unprecedented acrylonitrile yields. Researchers were able to achieve a 98% yield of acrylonitrile using a new, robust catalytic process.\u201d<\/p>\n
Direct Air Capture<\/p>\n
It\u2019s sexy stuff, direct air capture and CO2 removal from the sky. Hoovering the problem of climate change away, so to speak. A number of players are worth noting:<\/p>\n
As we reported last November, Swiss-based Climeworks launched a second-generation Direct Air Capture plant (DAC-3) in Troia, Apulia, it\u2019s third carbon capture plant so far. The new plant consists of three DAC collectors that use Climeworks\u2019 latest technology and require less energy than the plant they installed in Hinwil. The plant will filter up to 150 tons of CO2 from ambient air per year. Simultaneously, an alkaline electrolyser (1.2 MW) locally generates 240 cubic meters of renewable hydrogen per hour by making use of excess on-site photovoltaic energy. The captured CO2 and renewable hydrogen are then catalytically methanated (a process called Power-to-Gas) in modular reactors by French company ATMOSTAT.<\/p>\n
The news got hotter last month when we reported that Antecy\u2019s relevant assets in CO2 removal have been acquired by Climeworks and the business activities of both Antecy and Climeworks will be conducted through Climeworks AG, Switzerland.<\/p>\n
We profiled the field here in Solar fuels come nearer: Direct-from-air CO2 capture cost drops below $100\/ton threshold<\/p>\n
We profiled the field last week in Catch & Kill: the Velocys, Oxy, Cemvita, Carbon Engineering, BHP, Ginkgo chase to catch waste, kill emissions, armed with new organisms to liberate value.<\/p>\n
Multi Slide Guides to view:<\/p>\n
Carbon Capturing: The Digest\u2019s 2018 Multi-Slide ABLC Guide to Carbon Engineering<\/p>\n
Use it or Lose it: The Digest\u2019s 2019 Multi-Slide Guide to Waste Carbon Utilization<\/p>\n
The Bottom Line<\/p>\n
We might as well title this section, \u201cAoogah! Aoogah! Start-up company opportunity alert!\u201d<\/p>\n
A note here to the, uh, I think I counted it right, 35 companies I spotted recently in Emeryville, California when I opened the wrong car door and they all fell out. They dusted themselves off, cursed Zymergen and Pixar for soaking up every bit of empty space in the East Bay wide enough to fit a desk, and asked if I knew how to fit a start-up inside of a biobased straw.<\/p>\n
I did not, and off they took themselves in what I believe was the general direction of the Agile BioFoundry\u2019s virtual reality space inside the Berkeley Lab, which really ought to have one small room loaded with platinum catalyst talent and some metabolic pathway wranglers, identified as PtIXAR AMINATION, and therein to develop wondrous biobased amines of the future.<\/p>\n
Small companies could do worse things than focus amines, they might capture something as precious as CO2, which is to say, value, just sayin.<\/p>\n
<\/p>\n