About those biobased amines we might one day dream up at Ptixar Amination 

October 14, 2019 |

(Whoa Nelly! Just 24 hours after this story originally appeared, Nouryon dropped a new bombshell technology in this space, and you can read all about it here.)

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. 

And if you find something that blows up with great destructive force, you’ll find an amine in the mix (think, on the good side, automotive airbags, but you’ll find high energy explosives used in military operations at the rough stuff end of the spectrum). For that reason, they’re usually grouped with Yosemite Sam among the “meanest. roughest, toughest hombres that ever crossed the blood-brain barrier”. Or something like that.

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’ll know how powerful and vital CO2 removal technology can be, and that’s generally accomplished with amines.

As Michiel Pelckmans wrote in 2017 in a PhD thesis on the catalytic production of bio-based amines and derivatives:

Amines are…building 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…Moreover, 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.”

Biobased alternatives

Pelckmans provided this guide, noting:

“various 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).”

Catalyst advances

Beyond platinum, there’s ruthenium, which wouldn’t be exactly cheap. Nonetheless, researchers reported in Chemical Science last year:

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.”

Carbonyl compounds include a whole bunch of stuff, including aldehydes, carboxylic acids, amides — 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.

Who makes them thar amines?

When you ask yourself “who is the world leader in [pick your chemical of choice], the safe answer is usually “BASF”. And when it comes to amines, you never heard of so many brans in your life ending in “OR” “AR” UR” “OL” or “IL” until you’ve leafed through BASF’s amines and ethanolamines portfolio. 

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 — and as we read above, not always made via pretty green processes or intermediates you could soak your hands in. There’s a lot of BLAM! BLAM! in amines, or BLAMINE, if you will.

The markets are small-ish but the margins delightful — perfect targets for small biobased operations looking for a way forward in the years before they achieve world-scale commercial-scale. 

Who are the kings and queens of the clean green amine gene scene?

Let’s look into advances with inorganic catalysts and mighty microbes.

Among this year’s crop of research papers, we noted that researchers from the University of Bordeaux and the ArianeGroup highlighted:

“Bio-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.”

From Green Chemistry, let’s highlight this one:

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.

From a slightly older edition of the same journal, let’s highlight this one:

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. 

And this evergreen review for the year prior, published in Chemical Reviews:

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.

Who’s working on it?

The leader is, as noted above, BASF. And they’re doubling down on traditional sources, As we reported in April, “BASF 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’s 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.

“As one of the world’s 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”, said Dr. Andrea Frenzel, President, BASF Intermediates Division.

But others are in the mix, For example, Zymergen. We spotted a need for a polymer chemist a while back requiring “expertise in synthesizing amine-functional resins, polyols, epoxies, isocyanates, adhesion promotors, additives, and UV curable resins.”

Intermediates

As this review notes: 

Acrylamides are produced by the treatment of 3-HPA with an amine…polyacrylamide 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.

Which makes 3-HP and 3-HPA and amines a couple of targets of interest. As the researchers note, “3-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.” 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.

Though, we did report back in 2017 that “the 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.”

Direct Air Capture

It’s 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:

As we reported last November, Swiss-based Climeworks launched a second-generation Direct Air Capture plant (DAC-3) in Troia, Apulia, it’s third carbon capture plant so far. The new plant consists of three DAC collectors that use Climeworks’ 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.

The news got hotter last month when we reported that Antecy’s 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.

We profiled the field here in Solar fuels come nearer: Direct-from-air CO2 capture cost drops below $100/ton threshold

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.

Multi Slide Guides to view:

Carbon Capturing: The Digest’s 2018 Multi-Slide ABLC Guide to Carbon Engineering

Use it or Lose it: The Digest’s 2019 Multi-Slide Guide to Waste Carbon Utilization

The Bottom Line

We might as well title this section, “Aoogah! Aoogah! Start-up company opportunity alert!

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.

I did not, and off they took themselves in what I believe was the general direction of the Agile BioFoundry’s 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.

Small companies could do worse things than focus amines, they might capture something as precious as CO2, which is to say, value, just sayin.

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