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Bioenergy. Cellulosic ethanol. Patent Analysis

Aenert news. Invention analysis
Earlier, in the field of energy production from biomass, we published articles related to biomass gasification technologies – concerning pre-treatment of feedstock (04.03.2023) and disclosing advancements in fluidized bed reactors (31.01.2023).

This time we will revise technical solutions related to ethanol production from cellulosic biomass by analyzing patents published in the past 20 years and recent patent applications.

The documents in this collection were published in 54 patent offices around the world by 1547 applicants from 43 countries.

Bioenergy. Cellulosic ethanol. Cumulative number of patents and applications*, relationship of number of applications to total number of documents by year

Bioenergy. Cellulosic ethanol. Cumulative number of patents and applications

*Areas representing patents and applications are overlapping

In the collection of documents used for this analysis, the peak values in the number of granted patents were achieved in 2014-2019. In the case of patent applications, the highest number of registered documents was in 2014-2017, followed by a moderate decline. In recent years, the number of start documents that didn’t belong to any previously formed patent family was on a low level – about 12%.

The number of newly appearing applicants in the collection of documents was on the rise in 2008-2013 with a decline in the most recent years. Similar pattern can be seen in newly appearing IPC indices and patent offices that reached their uppermost values in 2008-2016 and 2012-2017, respectively. Considering a noticeable decline in the last years, a slowdown can be suggested in the patenting activity in the field of cellulosic ethanol production, both in terms of technological and geographical coverage.

During the twenty-year period, the largest number of patents were granted in USPTO (US) – more than 32% of all collected patents. It was followed by IP Australia (AU) – 11%, EPO – 9%, and CNIPA (CN) – 8%. In the collection of patent applications registered in the past 5 years, USPTO (US) also was in the lead with more than 22% of applications, followed by INPI (BR) – 12%, CNIPA (CN) – 11%, and EPO – 8%.

Bioenergy. Cellulosic ethanol. Breakdown of inventions by patent offices. Patents, 20 years (left); Applications, 5 years (right)

Bioenergy. Cellulosic ethanol. Breakdown of inventions by patent offices. Patents

The United States also holds the first position by being the country of residence for the largest number of applicants participating in the patenting process, having almost 58% of all cases in patents granted during the 20-year period, and almost 52% in the case of 5-year applications. In the case of patents, it was followed by the Netherlands (about 7%), and Denmark (almost 5%), while in applications – by the Netherlands (more than 11%), and China (almost 6%).

Below we provide a list of top 10 applicants with the highest Market involvement ratio for patents published in the 20-year period (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):

Bioenergy. Cellulosic ethanol. Top applicants by Market involvement ratio. Patents

StatusCountryNameVolume
ratio, %
Ownership
ratio, %
Market involvement
ratio, %
CompanyUSXyleco Inc.28.7298.5828.31
CompanyNLDSM IP Assets B.V.4.3391.143.95
CompanyDKInbicon A/S1.8592.541.71
OrganizationFRIFP (École Nationale Supérieure du Pétrole et des Moteurs)1.758.61.00
CompanyUSVerenium Corporation1.6181.891.32
CompanyNLShell Internationale Research Maatschappij B.V.1.4698.331.44
CompanyUSBASF Enzymes LLC1.2281.330.99
CompanyUSCargill Incorporated1.1783.020.97
CompanyUSPoet Research, Inc.1.1780.210.94
CompanyCHSyngenta Participations AG1.1761.60.72

 
In the collection of patents related to cellulosic ethanol production technologies, Xyleco Inc. (US) has a strong lead by the number of documents among all applicants – 590 documents. It is followed by DSM IP Assets B.V. (NL) – 89, Inbicon A/S (DK) – 38, IFP (École Nationale Supérieure du Pétrole et des Moteurs) (FR) – 35, and Verenium Corporation (US) – 33 documents. In terms of recently published patent applications, the leaders were Xyleco Inc. (US) – 554, DSM IP Assets B.V.(NL) – 138, API Intellectual Property Holdings LLC (US) – 39, Clariant International AG (CH) – 37, and Novozymes A/S (DK) – 37 patent applications.

Bioenergy. Cellulosic ethanol. Top applicants by Market involvement ratio. Applications

 

StatusCountryNameVolume
ratio, %
Ownership
ratio, %
Market involvement
ratio, %
CompanyUSXyleco Inc.34.0799.6233.94
CompanyNLDSM IP Assets B.V.8.491008.49
CompanyUSAPI Intellectual Property Holdings LLC2.41002.4
CompanyCHClariant International AG2.281002.28
CompanyDKNovozymes A/S2.2883.781.91
CompanyHULallemand Hungary Liquidity Management LLC1.9191.941.76
OrganizationFRIFP (École Nationale Supérieure du Pétrole et des Moteurs)1.646.150.74
OrganizationFRINRA  L'Institut national de la recherche agronomique1.3544.70.6
CompanyCAIogen Corporation1.291001.29
OrganizationFRLe Centre national de la recherche scientifique (CNRS)1.2332.080.39


Among the patents and patent applications describing technologies and equipment for cellulosic ethanol production, the most commonly mentioned problems are Low efficiency of main processes, High costs in general, and Low efficiency / Variety of feedstock. Methods and compositions are the types of technical solutions the inventors mainly chose for their inventions, while devices are encountered less often in the documents. The most popular IPC subgroups assigned to the patent documents were: C12P7/10 (substrate containing cellulosic material), C12P7/06 (Ethanol, i.e. non-beverage), C12P19/14 (produced by the action of a carbohydrase, e.g. by alpha-amylase), C12P19/02 (Monosaccharides), and C13K1/02 (obtained by saccharification of cellulosic materials).

The largest patent family of the entire collection made for the present analysis includes 339 patent documents and is represented by core document US10066339B2 (
Core document is a base document for which a complete description of the invention is available in generally-accessible patent databases):

Processing materials / P: US10066339B2 / IPC: B01D15/02, B01D53/32, B01D61/44, B01J19/08, B65G27/00, B65G53/04, B65G53/40, C07C29/149, C07C31/12, C10G1/00, C10L9/08, C12M1/00, C12P19/02, C12P19/14, C12P7/06, C12P7/10, C12P7/52, C13K1/02, C13K13/00, D21C9/00, G21F7/00, H01J37/317, E04B1/92 / Medoff Marshall, Masterman Thomas Craig, Paradis Robert / Xyleco Inc / Appl. date: 11.10.2017; Publ. date: 04.09.2018 / United States Patent and Trademark Office / Core document: US10066339B2 / Technology categories: CE / Technology elements: PP / Problems: LEVF / Technical solution types: D, M / Claims: 22 / Rating: 23

It is followed by patent families having 178 and 112 patent documents and represented by core documents US20150211730A1 and US20190139660A1, respectively:

Processing biomass / A: US20150211730A1 / IPC: F22B1/00, C10L1/02, F01K13/02, F01K7/16, F01K9/00 / Medoff Marshall / Xyleco Inc / Appl. date: 02.04.2015; Publ. date: 30.06.2015 / United States Patent and Trademark Office / Core document: US20150211730A1 / Technology categories: CE, PT / Technology elements: PTF / Problems: LEVF / Technical solution types: C, M / Claims: 20 / Rating: 16

Processing biomass / A: US20190139660A1 / IPC: G21F3/00, A61L2/08, B01J19/08, B01J19/12, B01J19/22, B65G27/04, C08H8/00, C10B19/00, C10B53/02, C10G1/02, C10G32/04, C10L5/40, C10L5/44, C10L5/46, C13K1/02, C13K13/00, D21B1/02, G21K5/04, G21K5/10, H01J5/18, H01J33/04, H01J37/20, H01J37/317 / Medoff Marshall, Masterman Thomas Craig, Paradis Robert / Xyleco Inc / Appl. date: 01.11.2018; Publ. date: 09.05.2019 / United States Patent and Trademark Office / Core document: US20190139660A1 / Technology categories: AL, CE / Technology elements: PTF, SE / Problems: HCG, LEMP / Technical solution types: M / Claims: 15 / Rating: 18


The following abbreviations are used in the documents hereinbefore and hereinafter: C - Composition; D - Device; M - Method; CE - Cellulosic ethanol; PT - Pyrolysis & torrefaction; AL - Algae; LEVF - Low efficiency / Variety of feedstock; LEMP - Low efficiency of main processes; HCG - High costs in general; PTF - Pre-treatment of feedstock; PP - Primary processing; SE - Secondary equipment.

Bioenergy. Cellulosic ethanol. Breakdown of documents by family size. Patents and applications

Bioenergy. Cellulosic ethanol. Breakdown of documents by family size

The following are examples of patents with the highest rating calculated in accordance with the Advanced Energy Technologies methodology in the collection of patent documents related to ethanol production from cellulosic biomass:

Bioenergy. Cellulosic ethanol. Prominent patent documents by rating:

Treating Biomass / P: US10510510B2 / IPC: H01J37/317, B01J19/08, C10L1/02, C12P19/02, C12P19/14, G21K5/04, G21K5/10, H01J5/18, H01J7/26, H01J33/04 / Medoff Marshall, Peters Anthony, Masterman Thomas Craig, Paradis Robert, Ip Kenny Kin-chui / Xyleco Inc / Appl. date: 13.04.2017; Publ. date: 17.12.2019 / United States Patent and Trademark Office / Core document: US9659748B2 / Technology categories: AL, CE / Technology elements: PTF, SE / Problems: HCG, LEMP / Technical solution types: C, D, M / Claims: 45 / Rating: 25

Treating biomass / P: US9659748B2 / IPC: H01J37/317, B01J19/08, C10L1/02, C12P19/02, C12P19/14, G21K5/04, G21K5/10, H01J5/18, H01J7/26, H01J33/04 / Marshall Medoff, Anthony Peters, Thomas Craig Masterman, Robert Paradis, Kenny Kin-Chui IP / Xyleco Inc / Appl. date: 10.10.2013; Publ. date: 23.05.2017 / United States Patent and Trademark Office / Core document: US9659748B2 / Technology categories: AL, CE / Technology elements: PTF, SE / Problems: HCG, LEMP / Technical solution types: C, D, M / Claims: 63 / Rating: 25

Treating biomass / P: AU2013329153B2 / IPC: B01J19/08, C12P19/00, G21K5/10 / Marshall Medoff, Anthony Peters, Thomas Craig Masterman, Robert Paradis, Kenny Kin-Chui IP / Xyleco Inc / Appl. date: 10.10.2013; Publ. date: 14.09.2017 / IP Australia / Core document: US9659748B2 / Technology categories: AL, CE / Technology elements: PTF, SE / Problems: HCG, LEMP / Technical solution types: C, D, M / Claims: 43 / Rating: 25

Treating biomass / P: AU2017276162B2 / IPC: B01J19/08, C12P19/00, G21K5/10 / Peters Anthony, Medoff Marshall, Masterman Thomas Craig, Paradis Robert, IP Kenny Kin-Chui / Xyleco Inc / Appl. date: 11.12.2017; Publ. date: 24.10.2019 / IP Australia / Core document: US9659748B2 / Technology categories: AL, CE / Technology elements: PTF, SE / Problems: HCG, LEMP / Technical solution types: C, D, M / Claims: 24 / Rating: 25

Processing materials / P: US9789461B2 / IPC: A61L11/00, B01D39/18, B01J19/08, B65G27/04, D21B1/02, G21K5/10, H01J37/20 / Medoff Marshall, Masterman Thomas Craig, Paradis Robert / Xyleco Inc / Appl. date: 29.03.2017; Publ. date: 17.10.2017 / United States Patent and Trademark Office / Core document: US20190139660A1 / Technology categories: AL, CE / Technology elements: PTF, SE / Problems: HCG, LEMP / Technical solution types: M / Claims: 20 / Rating: 24

Treating biomass / P: PH12015500410B1 / IPC: B01J19/08, C10L1/02, C12P19/02, C12P19/14, G21K5/04, G21K5/10, H01J5/18, H01J7/26, H01J33/04, H01J37/317 / Peters Anthony, Medoff Marshall, Masterman Thomas Craig, Paradis Robert, IP Kenny Kin-Chui / Xyleco Inc / Appl. date: 25.02.2015; Publ. date: 20.04.2015 / Intellectual Property Office of the Philippines / Core document: US9659748B2 / Technology categories: AL, CE / Technology elements: PTF, SE / Problems: HCG, LEMP / Technical solution types: C, D, M / Claims: 0 / Rating: 24

電子ビーム加速器の窓箔を冷却するためのシステムおよび方法 (en: System and method for cooling a window foil of an electron beam accelerator) / P: JP6638010B2 / IPC: G21K5/00, B09B5/00, G21K1/04, G21K5/04 / Peters Anthony, Medoff Marshall, Mastenrman Thomas Craig, Paradis Robert, Ip Kenny Kin-chui / Xyleco Inc / Appl. date: 01.03.2018; Publ. date: 29.01.2020 / Industrial Property Office / Core document: US9659748B2 / Technology categories: AL, CE / Technology elements: PTF, SE / Problems: HCG, LEMP / Technical solution types: C, D, M / Claims: 53 / Rating: 24


In the collection of patents and patent applications related to ethanol production from cellulosic ethanol, the majority of documents disclose technical solutions related to Pre-treatment of feedstock that implies preparation of diversified feedstock for further processing, Primary processing involving the production of ethanol from cellulosic feedstock, and Chemistry and other substances used in the preparation of ethanol. Below we revise several examples of inventions that concern these groups of technical solutions.

- US10704196B2 - a feedstock preparation process involving reducing the dimensions of pieces, irradiating with electron beam to increase brittleness, milling to further reduce the dimensions of feedstock pieces mechanically. Used to improve the applicability of feedstock in ethanol or other fuel production technologies;

- US11434508B2 - improved cost-efficiency of lignocellulosic material hydrolysis is achieved by a two-step process involving an enzyme composition with at least two cellulases, including GH61, for example, fungus-derived Rasamsonia emersonii enzyme;

- US9580729B2 - method for producing ethanol from lignocellulosic biomass involves pre-treatment, cellulose hydrolase treatment, fermentation, and solid-liquid separation. The cycle is repeated at least twice with yeasts being efficiently reused in subsequent cycles, which reduces the overall cost of the process;

- US10066244B2 - efficient and economical ethanol production from cellulosic material is achieved by a process with enzymatic saccharification and fermentation steps, in which one or more enzymes are selected from a variety of options, and a specific strain of Saccharomyces cerevisiae, called CIBTS1260 is used for fermentation;

- US10619147B2 - improved ethanol production from cellulosic biomass by using a chimeric polypeptide having xylose isomerase activity.



Pre-treatment of feedstock

Patent US10704196B2 published by Xyleco Inc discloses a method for preparing cellulosic and lignocellulosic biomass feedstock for conversion into ethanol or butanol. The method involves reducing the dimensions of individual pieces of the feedstock, irradiating it with electron beam radiation at a dose rate of at least 1.0 Mrad/sec to increase brittleness of the feedstock, mechanically reducing the dimensions of the irradiated feedstock (for instance, by milling), and then converting it to a product. The claims include several specific features of the treated biomass feedstock: it has uncompressed bulk density of less than about 0.6 g/cm3, and includes fibers having a length/diameter (L/D) ratio of at least about 5. The feedstock can comprise paper wastes, wood wastes, agricultural wastes, algae, etc.

The invention is aimed at processing the feedstock so that it can be more readily utilized in the productions of useful products, such as fuel.

The patent belongs to a family comprising 225 patent documents published between 2008 and 2020 in such patent offices as AP, AU, BR, CA, CN, EA, EP, IL, JP, KR, MX, NZ, RU, SG, US, WO, and ZA.


Image from: US10704196B2

100 - system for converting biomass; 110 - feed preparation subsystem; 114 - pretreatment subsystem; 118 - primary process subsystem; 122 - post-processing subsystem.


Patent US11434508B2 published on 06.09.2022 by DSM IP Assets BV describes a process for preparing sugar and fermentation products from lignocellulosic material by hydrolysis using an enzyme composition comprising at least two cellulases, including GH61. The hydrolysis occurs in two steps, with more oxygen being added during the second step, which is 2%-80% of the total enzymatic hydrolysis time. The oxygen is preferably added to the lignocellulosic material in the form of air bubbles. The hydrolysis is performed in a batch, fed batch and/or continuous culture reactor having a volume of 1 m3 or more, during 5-150 hours at 45°C or more. The enzyme composition retains activity for at least 30 hours, and is preferably derived from a fungus, for instance, Rasamsonia emersonii enzyme. Dry matter content in the hydrolysis process is preferably 14 to 33% wt %.

With regard to prior-art solutions, the authors mention high costs required for production of enzyme compounds in ethanol production technologies and are aimed at improving the hydrolysis process.

The patent is a part of a patent family comprising 72 documents, published in CA, WO, AU, CN, KR, MX, EA, EP, BR, IN, US, JP, UA, and MY in 2014-2023.



Image from: US11434508B2



Primary processing

A method for producing ethanol from lignocellulosic biomass is proposed in patent US9580729B2 by Kansai Chemical Engineering Co., Ltd, (JP) and Bio-energy Corporation (JP). The method includes pretreating the biomass, treating the resulting cellulose fraction with a cellulose hydrolase, mixing the resulting saccharified biomass slurry with yeasts for ethanol fermentation, and subjecting the fermented product to solid-liquid separation. The solid-liquid separation step includes removing a solid content to obtain residues, and collecting a solid content of the residues, constituting 5% to 30% by mass of the fermented product. This cycle is repeated at least twice, and yeasts obtained in the solid-liquid separation step are used in a subsequent cycle, "…wherein the yeast is transformed so as to express one or two enzymes selected from the group consisting of ferulic acid esterase, β-glucosidase, β-galactosidase and pectinase". The yeast concentration in the fermented product is at least 107 cells/mL, and the enzyme can be displayed on the yeast cell surface. The fermented product contains yeast, ethanol, lignin, and ash content derived from the biomass.

According to the authors of the invention, efficient reuse of yeasts in different fermentation steps decreases the overall costs of ethanol production from lignocellulosic biomass.

The invention belongs to a patent family that comprises 7 documents published in 2013-2018 in the WO, US, IN, JP, and MY patent offices.



Image from: US9580729B2



Chemistry and other substances

Patent US10066244B2 by Novozymes A/S (DK) discloses a process for producing ethanol from an optionally pre-treated cellulosic material by saccharifying it with a cellulolytic enzyme composition and fermenting it with a specific strain of Saccharomyces cerevisiae, called CIBTS1260. The fermentation product is then recovered from the fermentation. The cellulolytic enzyme composition may comprise one or more enzymes selected from "…a cellulase, an AA9 polypeptide, a hemicellulase, a CIP, an esterase, an expansin, a ligninolytic enzyme, an oxidoreductase, a pectinase, a protease, and a swollenin". The saccharification and fermentation steps may be performed simultaneously or sequentially. The process can be performed with a recombinant fermenting organism having the same properties as Saccharomyces cerevisiae CIBTS1260 and being capable of specific levels of xylose consumption, glucose consumption, and ethanol production, as stated in the claims.

The authors point out the need in a more economically viable and biologically efficient process.

The invention belongs to a patent family comprising 13 documents published between 2016 and 2022 in the CA, WO, AU, MX, EP, CN, US, and BR patent offices.



Image from: US10066244B2

Patent US10619147B2 proposes a chimeric polypeptide having xylose isomerase activity and methods of fermenting cellulosic biomass to biofuels, including ethanol. The chimeric polypeptide comprises "…an amino acid sequence having at least 95% sequence identity with an amino acid sequence of SEQ ID NO: 27". The chimeric polypeptide further comprises specific amino acid sequences at positions 188-196 and 233-240 and three specific amino acid residues at positions 103, 106, and 341. The invention also describes a method of synthesizing the polypeptide comprising transforming a yeast cell with parent polynucleotide sequences and a linearized vector, where the parent polynucleotide sequences form a chimeric polynucleotide encoding, and "…screening the transformed yeast cells for said recombination wherein said chimeric polynucleotide encodes said chimeric polypeptide". Ethanol is produced by contacting a xylose feedstock with the polypeptide.

The inventors mention the need to convert the majority of sugars into ethanol.

The patent is a part of a family comprising 10 patent documents published in US, CA, WO, MX, CN, EP, and BR in 2016-2021.



Image from: US10619147B2

During the analysis of these and other inventions from the collection of patent documents it was revealed that the two major challenges in cellulosic ethanol production are insufficient conversion of biomass feedstock or sugars derived therefrom into ethanol and particularly negative impact of feedstock diversity on the efficiency of conversion process. These two problems were widely and continuously addressed by the authors of inventions for more than a decade and will probably be on the agenda in the future.

More detailed information about inventions in the field of bio energy, and patent research methodology can be found on aenert.com, in BIOENERGY. Biomass Gasification. Extended patent report. September 2021, and BIOGAS. Feedstock, Production, Treatment. Patent Database. July 2021.


By the Editorial Board