Hydrogen

Aenert news. Invention analysis
Previously, we already published several articles on recent patenting activity in the field of liquid organic hydrogen carriers (LOHC). Back then we have covered several individual aspects of the technology, namely aromatic (29.09.2023) and heterocyclic (08.09.2023) LOHC compounds, hydrogenation and dehydrogenation (30.10.2023 and 17.10.2023), and catalysts (20.11.2023).

Today we bring to your attention a more in-depth review on LOHC catalysts, namely, a review of recent patents on LOHC catalysts that use noble metals as the active material. Generally, noble metals play a crucial role in catalysis due to their unique properties that make them effective catalysts in various chemical reactions. The term "noble metals" typically refers to such metals as platinum, palladium, ruthenium, gold, and others. Noble metals exhibit high catalytic activity due to their beneficial structural characteristics, high reactivity, and selectivity. They can accelerate chemical reaction at relatively low temperatures, are resistant to corrosion, and have high durability and versatility. However, noble metals also have drawbacks, such as high cost and limited availability.

Below we provide a brief review of recent inventions disclosing the use of noble metal catalysts in Liquid Organic Hydrogen Carrier technologies. The patents selected for this review include such patents, where noble metals are main active catalytic material, are proposed as one of the options, or used in combination with other materials. The inventions may also disclose other aspects of LOHC storage and transportation technology, such as hydrogenation and dehydrogenation processes, and the like.

Following is a list of the top applicants by their patenting share in the field of LOHC catalysis.

Applicants share in the intellectual property market, percentage. Patents, 2019-2023



Value: Market involvement ratio*; Y axis: Ownership ratio; Bubble size: Volume ratio.
*(Market involvement ratio = volume ratio multiplied by ownership ratio, where Volume ratio - share of applicant documents in total number of documents, Ownership ratio - applicant's participation share in total number of documents)

In the revised set of documents, Sinopec China Petroleum & Chemical Corporation (CN) and its affiliated organizations, Energystoredge Ltd (IL), and Yissum Research Development Company of the Hebrew University of Jerusalem Ltd (IL) are leading by the number of patents obtained in the past five years.

In the collection of documents under consideration, the largest patent families comprise 31, 14, and 12 patent documents and are represented by core documents AU2020269473A1, WO2020224584A1, and US10944119B2, respectively (Core document is a base document for which a complete description of the invention is available in generally-accessible patent databases):

Organic hydrogen storage raw material dehydrogenation catalyst, carrier of the catalyst, hydrogen storage alloy, and method for providing high-purity hydrogen / A: AU2020269473A1 / IPC: C22C19/03, C01B3/56, C22C14/00, C22C23/06, C22C30/00 / Lin Wei; Yang Xue; Song Haitao; et al. / Sinopec RIPP Research Institute of Petroleum Processing (CN); Sinopec China Petroleum & Chemical Corporation (CN) / Appl. date: 06.05.2020; Publ. date: 12.11.2020 / IP Australia / Core document: AU2020269473A1 / Technology categories: OAC, OHC / Technology elements: Hdh, Hct / Problems: EC, HCHD, LEHD / Technical solution types: M, C / Claims: 16 / Rating: 13; the most recent documents in this family were published on 15.11.2022 (CN111892016B) and 21.10.2022 (CN111893360B);

有机储氢原料脱氢催化剂以及该催化剂的载体、储氢合金、和提供高纯度氢气的方法 / en: Catalyst for dehydrogenating organic hydrogen storage raw material, carrier for catalyst, hydrogen storage alloy, and method for providing high purity hydrogen / A: WO2020224584A1 / IPC: B01J23/26 / Lin Wei; Yang Xue; Song Haitao; Sun Min / Sinopec China Petroleum & Chemical Corporation (CN); Sinopec RIPP Research Institute of Petroleum Processing (CN) / Appl. date: 06.05.2020; Publ. date: 12.11.2020 / World Intellectual Property Organization / Core document: WO2020224584A1 / Technology categories: OAC, OHC, OAN / Technology elements: Hdh, Hct / Problems: LEHD / Technical solution types: M, C / Claims: 14 / Rating: 10; the most recent documents in this family were published on 21.10.2022 (CN111892018B) and 15.07.2022 (CN111895266B);

Methods and devices for storage and release of hydrogen / P: US10944119B2 / IPC: H01M8/06, H01M8/04082, B01J7/02, H01M8/04089, H01M8/0612, C01B3/22, C01B3/00 / Sasson Yoel; Toubiana Judith; Givant Ariel; Rothschild Sorel / Yissum Research Development Company of the Hebrew University of Jerusalem Ltd (IL); Energystoredge Ltd (IL) / Appl. date: 13.05.2016; Publ. date: 09.03.2021 / United States Patent and Trademark Office / Core document: US10944119B2 / Technology categories: OAC / Technology elements: Hdh, Hct / Problems: EC/ Technical solution types: M, C / Claims: 22 / Rating: 4; the most recent documents in this family were published on 01.02.2022 (IL255535B) and 24.08.2021 (CN107848794B).

The following abbreviations are used in the documents hereinbefore and hereinafter: C - Composition; M - Method; OAC - Arene/Aromatic compound; OAN - Amine; OHC - Heterocyclic; EC - Ecological problems; HCHD - High cost of hydrogenation or dehydrogenation; LEHD - Low efficiency of hydrogenation or dehydrogenation; Hct - Catalyst; Hdh - Dehydrogenation.

Authors of the patents on catalytic materials involving noble metals generally refer in their patent inventions to the following problems: High cost or low efficiency of catalyst, Low efficiency of hydrogenation or dehydrogenation, and High cost of hydrogenation or dehydrogenation.

In the majority of cases, technical solutions disclosed in the collection of inventions under revision are represented in the form of compositions. Methods are proposed a little less often, while devices are not provided at all.

In the list of noble metals used as active catalytic materials in the inventions, palladium holds a second place by popularity after platinum. Following is a brief statistical review of such inventions describing LOHC catalysts having palladium as the active material. In these documents palladium can be the only active material proposed by the inventors, be one of the suggested options, or be in combination with other elements.

In the majority of cases, the following IPC indices were assigned to the inventions describing palladium-based LOHC catalysts:
 

According to the International Patent Classification, the IPC indices above have the following definitions: C01B3/00 - Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; B01J23/89 - combined with noble metals; B01J23/44 - Palladium; B01J23/46 - Ruthenium, rhodium, osmium or iridium; B01J23/42 - Platinum; C22C30/00 - Alloys containing less than 50% by weight of each constituent; C01B3/56 - by contacting with solids; Regeneration of used solids; C07C11/09 - Isobutene; C07C5/333 - Catalytic processes; C07D209/86 - with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system.

By the number of patents granted in this category of inventions, CNIPA (CN) patent office is at the top of the table having about 74% of all patents. It is followed by JPO (JP), KIPO (KR), and USPTO (US).

Further, we reviewed, to which problems authors of the inventions on palladium catalysts address in their patents. The most popular problems here were poor process efficiency in general (12 patents), purity of H₂ product (9 patents), catalyst stability in terms of durability (8 patents), low pressure of H₂ product (8 patents), low catalyst efficiency in terms of activity rate of catalytic materials (7 patents), and extensive use of precious materials (6 patents).

By the Editorial Board