History & Patents
A personal history and status of the Technology
Paul O’Connor april ’22
A few years ago, I ran into my old friend Doug Cameron at a conference where I was presenting a paper on the technological innovations of ANTECY. These were aimed to produce green “Solar” fuels converting CO2 from the air into methanol and/or other liquid fuels making use of green hydrogen produced from Solar, Wind, Ocean and/or hydrothermal energy. Doug had introduced me to Vinod Khosla years ago (~2006), and thereafter Khosla Ventures invested into KiOR; a joint venture with my first start-up BIOeCON. Unfortunately, the KiOR venture based on catalytic pyrolysis of biomass was not a success.
Doug asked me if I knew a way how to crack Methane to Hydrogen. He informed me that several groups were working on this making use of molten metals at very high temperatures whereby the Carbon is extracted from the Methane molecule and can be separated from the molten metals as the light Carbon will float on the surface of the heavier metal melt.
The intention would be to convert Methane into Hydrogen without producing CO2. The reason he asked my advice was because he knew of my long background and career in catalysis, mainly Fluid Catalytic Cracking (FCC) and of course also Catalytic Pyrolysis.
I remembered that in my early days at AkzoNobel (~1985), I had also worked shortly on Catalytic Coking, mentored by the late Dr. J.I (Jan) de Jong or “J.I” as we all called him with great love and respect. We had then concluded that any catalyst that worked, would instantly coke itself up, meaning that it would deactivate very fast and making it ineffective.
However, at the time we were solely working with solid catalysts, like FCC catalyst. I started thinking about the possibility of using a liquid catalyst that would be less susceptible to deactivation by coking and whereby it would be easy to separate the coke from the liquid catalyst. I recalled the early history of FCC where in the 1920’s Mr. McAfee (not from the virus checker) developed a process to crack hydrocarbons, making use of Aluminum Chloride as a molten salt. [1].
At the end of 2005 I left Albemarle, who had acquired Akzo Nobel catalysts, and formed my first start-up venture BIOeCON, which focuses on the conversion of biomass waste into fuels and chemicals. The foundational idea was to use the FCC process to convert solid biomass with a solid catalyst by firstly forming an intimate composite to overcome the challenge of a poor effective accessibility of the active sites [2].
In BIOeCON we also developed a second novel technology (2007-2008) using molten salts, mainly Zinc Chloride hydrate to fractionate and convert biomass into fuels and chemicals [3]. Subsequently, we also applied these modified molten salts (2016) to separate biomass and convert it into high value cellulose (Nano-cellulose) and clean lignin. The latter technology is now being commercialized by CELLiCON [4].
Shortly after (2017), I came up with the idea to use molten salt technology and certain modifications thereof to produce Hydrogen from hydrocarbons such as Methane, making use of its catalytic properties and of the flexible and successful separation of the Carbon produced from the molten salts [5]. The patent was filed by ANTECY as my thought was that the Hydrogen produced in this way would be suitable to produce green fuels like Methanol by using CO2 from Direct air Capture.
In 2019 CLIMEWORKS acquired the technology and IP from ANTECY, including the aforementioned patent. Meanwhile I continued looking for funding to develop this idea which I called CarbonPlus. In addition I wanted to search for more applications in some new areas, such as for the Carbonization of biomass waste, textile wastes and/or plastics. Tony Picaro who I had met at a conference on CO2 reduction in my ANTECY days, strongly promoted the idea of looking at plastic and/or mixed wastes.
As mentioned on this website, capturing and sequestering the CO2 emitted from burning biomass wastes can be converted into a CO2-zero emissions state at the cost of about $60 per ton CO2, which is lower than the costs of Direct Air Capture of CO2, which is estimated to be in the $100-200 per ton CO2 at large scale. Moreover, current waste to energy/fuels or waste to products processes are energy intensive and there is a concern that they generate high volumes of hazardous waste and toxic emissions, e.g., from plastic waste recycling.
Early 2021 I came across Siemon van de Berg who was interested in promoting new breakthrough technology ideas for improving the environment. I presented CarbonPlus and received a first grant from CarbonFix (www.carbonfix.org), which resulted in the formation of YERRAWA.
YERRAWA has obtained a license of the patent now owned by Climeworks for the catalytic carbonization of methane to Hydrogen and Carbon. Carbonization of biowaste, plastics and/or mixed wastes requires several innovations which have been described in new patent applications filed by YERRAWA.
Carbon Plus technologies enable the conversion of biomass waste and synthetic organic waste to solid carbon and hydrogen in the presence of molten salt catalyst (ZnCl2) under milder conditions compared to competing technologies (hydrothermal liquefaction and pyrolysis/gasification processes). The formed solid carbon is easily separated from the reaction media and the molten salt catalyst is recycled to the reactor.
Our R&D results indicate that our Carbon Plus technology processing bio-waste results in a high solid carbon yield, while a high percentage of the nitrogen in feedstock is fixed in the solid carbon, making it a very interesting route to reduce Nitrogen (NOx, NH4) emissions.
Our next goal is to further demonstrate the technology for the carbonization of biomass waste as well as synthetic organic wastes in a bench scale laboratory environment, and to confirm the quality and value of the products, the overall techno-economics and LCA of the process.
English