A. Catalytic conversion of CO2

We invented a new technology to get para-xylene (PX) directly from CO2 or CO, accomplishing 6 synthesis steps via single step in only one catalyst pellet containing capsule catalyst, the first time in the world.


PX is a main monomer of polyester fiber and PET plastics, with an annual demand of 49 million ton worldwide. If all PX from petroleum now is tuned to be made from CO2, 0.16 billion ton CO2 will be fixed every year.
We aim to commercialize this CO2-to-PX novel technology before 2028 with the aid of NEDO, Japanese government. The consortium includes Tsubaki lab. at Univ. Toyama, Nippon Steel Co., Nippon Steel Engineering Co., HighChem Co., Chiyoda Co., Mitsubishi Co..
Tsubaki et al invented the direct synthesis technology of para-xylene (PX)/PET from CO2 for the first time in the world and it is now under scale-up. The zero-carbon PX/PET produced in pilot plant in Yokohama city of Chiyoda Corp. is now used to fabricate the zero-carbon uniform with the highly-ranked fashion brand " The North Face ", by the Toyama-initiated Goldwin Company who produces and sells this brand worldwide. Now this carbon-neutral PET uniform is commercially being sold for the first time in the world. Especially, this zero-carbon uniform is adopted as official uniform for Japan team of sport climbing in Paris Olympic Games 2024. Meanwhile, USA team, Korea team and Austria team will also use this uniform in sport climbing contest of Paris Olympic Games started on August 5, 2024 at PM5, Japan time. See Figures 1-5 below.

https://about.goldwin.co.jp/news/page-36620


Figure 1.Zero-carbon PET fiber uniform, the first time in the world, for Japan sport climbing team to Paris Olympic Games 2024


Figure 2.Zero-carbon PET-based uniform for Japan, USA, Korea, Austria teams to Paris Olympic Games 2024, sport climbing contest.


Figure 3.The first case in the world, zero-carbon uniform by The North Face produced for Japan sport climbing team to Paris Olympic Games 2024


Figure 4.Global partners in this new carbon-neutral business


Figure 5.The new carbon-neutral technology initiated from Tsubaki lab and Japan; I considered this idea in 2011.


Now the zero-carbon PET uniform, including kid style, is being sold at the Tokyo-Harajuku shop, Tokyo-Ebisu Shop, Osaka Grand Front shop etc. of The North Face. Net shopping is also available as the link below. See the Figures 6-9.

https://www.goldwin.co.jp/tnf/special/wallhuman/2024/article/international-collection-for-2024/


Figure 6. Goldwin Co. sells the carbon-neutral products for the first time in the world.


Figure 7.NEDO X SNS report


Figure 8.Report by Nikkei (Japan Economy Newspaper)


Figure 9.Press-release by Goldwin Co.


Related papers:
Chemical Science, 2017 isyngas CO+H2 PX jZn-Cr-O/ZnZSM5@S-1 capsule catalyst
Chemistry - A European Journal, 2019 iCO2 PX catalyst j
ACS Catalysis, 2019 iCO2 PX jCrOx/HZSM5@S-1 capsule catalyst

Other related papers:
CO2 to gasoline by capsule catalyst, Catal. Sci. Tech. 2019, ChemComm 2016
CO2 to diesel, ACS Sustainable, Chem. Eng., 2019
CO2 to LPG by capsule catalyst, ChemSusChem, 2020
CO2+methane to syngas (CO+H2), Chemical Science, 2019
CO2 to olefins, ChemComm, 2020
CO2 to aromatics, App. Catal. B, 2020

B. New FT (Fischer-Tropsch) synthesis technology

Developing Co/Al2O3@H-beta capsule catalyst to realize iso-paraffin (premier gasoline) direct synthesis from syngas (CO+H2), Angew. Chem., 2008
For the first time in the world, directly synthesizing jet fuel from syngas with Co/Ymeso-La catalyst, and building up a new anti-ASF mathematic model to quantitatively predict and elucidate. Nature Catalysis, 2018. Nature (editorial), 2018.




One-step synthesis of light olefins from syngas using Zn-Cr-O@SAPO34 capsule catalyst, Chemical Science, 2020.

C. New low-temperature methanol synthesis from hydrogenation of CO, CO,2

@The present industrial methanol synthesis from CO2 or CO hydrogenation is a very famous low-efficiency process, as it is thermodynamically-limited at high temperature and kinetically-limited at low temperature. Very high temperature, high pressure, excessive hydrogen are all necessary to get still low one-pass conversion in the present old technology. We invented a new method, borrowing a methanol to produce two methanol quickly at low temperature such as 130 oC and low pressure, with very high one-pass conversion. Acc. Chem. Res., 2013. J. Catalysis, 2001.


@We are now trying to commercialize CO2 to methanol with this new technology with Japanese companies.

D. BTL (biomass to liquid), GTL plants

D-1 Natural gas to diesel via syngas


@Bench plant in Tsubaki lab, Univ. Toyama (photo above), 10BPD (Barrel per Day) pilot plant in Hokkaido, 500BPD i80000L/D diesel j demonstration plant in Niigata city.


@D-2 @Bio diesel plant from fruit or wine biomass via gasification in Yamanashi city (photo below).




@D-3 @Rice husk gasification and Bio FT synthesis to bio-diesel plant in Akita city. Capacity is 4.5BPD. (photo below)





@D-4 @Biomass gasification and Bio jet fuel synthesis plant in Mitsubishi Heavy Industry Company, Nagasaki city factory. Capacity is 240kg/D.
Aiming to be poured into MRJ airplane of the Mitsubishi Heavy Industry Company. (photo below)




@D-5. As a Japanese government Official Development Assistance (ODA) project, being co-sponsored by Japan International Cooperation Agency (JICA) and Japan Science and Technology Agency (JST), we built a biomass conversion plant in Saraburi County, Thailand. Bio-diesel, gasoline (capsule catalyst), LPG (capsule catalyst), methanol (new low-temperature method) are produced from this plant using the new catalysis technologies of Tsubaki lab.. We thank the efforts from our partners: Japan Coal Energy Center (JCOAL), ENEOS Co., TOMOESHOKAI Co., Chulalongkorn University, PTT Co., NRE Co., JICA Thai Branch, etc.. (photo below)

E. Novel catalyst preparation method

Sputtering technology in catalyst preparation. Science Advances, 2018. Scientific Reports, 2013. ACS Catalysis, 2014. Chemical Science, 2019

Auto combustion method for reduction-free catalyst preparation. Journal of Catalysis, 2013. ACS Catalysis, 2011

SiC monolith 3D catalyst. Applied Energy, 2013

Hollow sphere catalyst. Journal of Materials Chemistry A, 2013

Graphene catalyst. ChemSusChem, 2014

Carbon nanotube catalyst. Chemistry?A European Journal, 2017. ACS Catalysis, 2012

Biomass-inspired catalyst. Chemistry?An Asian Journal, 2017. ChemCatChem, 2015

Bimodal catalyst. ChemComm, 2002. AIChE Journal, 2005

F. Capsule catalysts realizing new C1 chemistry synthesis

CO+CO2+H2 to DME idimethyl ether j one-step synthesis using Cu-Zn-Al-O@HZSM-5 capsule catalyst. J. Am. Chem. Soc., 2010
Glycerin hydrogenolysis to C3-diol using Ru/Al2O3@Pd@S-1capsule catalyst. Chemical Science, 2013
One-step synthesis of ethanol from DME and syngas (CO+H2) employing Cu-Zn-O@Cu-mordenite capsule catalyst. ACS Catalysis, 2020. In 2009, we reported direct synthesis of ethanol from DME and syngas (CO+H2) firstly in the world. Energy and Fuels, Vol.23, 2843-2844, 2009. Now this technique is being commercialized in several countries.
As an extension of capsule catalyst, we innovated water-melon-like Co@mesoSiO2 catalyst, breaking the classical rules of Fischer-Tropsch synthesis. Interestingly we disclosed that smaller cobalt nanoparticles can reversely produce longer-chain hydrocarbons. These findings can save expensive cobalt (due to Li ion battery) amount in catalysts at huge Fischer-Tropsch synthesis plants. Nature Communications, 2018. (Photo below)

G. 3D print technology in catalysis

Tsubaki et al invented metal 3D printed tubular catalytic reactor, named as self-catalytic reactor where the tailor-made complicated inner surface after activation serves as catalyst, for the first time in the world. This kind of novel self-catalytic reactor need not load catalyst and can be minimized significantly to fabricate micro-reactors. On-board, on-ship, or on-ocean compact chemical factory is realizable. (Nature Communications, 2020. Patent of Univ. Toyama and Nippon Steel Co., photo below)

H. Direct conversion of methane, shell gas, natural gas

@Methane to benzene using hollow MoCx/HZSM5 capsule catalyst. Journal of Materials Chemistry A, 2017
@Direct conversion of liquid natural gas (LNG) by plasma pulse. Applied Energy, 2013

I. Carbon-neutral tire synthesis from CO2

We invented another world-first carbon-neutral technology, CO2 to butadiene and carbon-zero tire synthesis recently. This technology is now being scaled up with Toyo Tires company. We plan to use these carbon-neutral tires to enter Paris-Dakar desert Rally. Please refer to the following slides 1-4.





Related papers from our lab::
CO2 to ethanol, ACS Catalysis, 2021
CO2 to ethanol, Chem. Soc. Rev., 2022
Ethanol to butadiene, Applied Catalysis B, 2022
Zeolite catalyst for ethanol synthesis, Nature Comm., 2022
CO2 to ethanol, Angew. Chem., 2023
CO2 to ethanol, Angew. Chem., 2023
CO2 to LPG or olefins, Nature Comm., 2024
CO2 to butadiene, Chem, 2024

2021 January version

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